Method for producing 1,2-dichloro-3,3-difluoro-1-propene and solvent composition

ABSTRACT

By fluorinating 1,2,3,3-tetrachloro-1-propene (1230xd) using hydrogen fluoride as a fluorinating agent, an efficient method for producing 1,2-dichloro-3,3-difluoro-1-propene (1232xd) is provided. Through this composition including 1232xd, there are also provided an environmentally friendly composition having excellent ability to dissolve various organic matters, a method for cleaning an article using the composition, a method for producing a lubricant solution using the composition, and a method for producing a component provided with a lubricant coating film.

CROSS REFERENCE TO RELATED APPLICATION

This application is based upon and claims the benefit of priority fromthe prior Japanese Patent Application No. 2018-026033, filed on Feb. 16,2018. Further, this application is the National Phase Application ofInternational Application No. PCT/JP2019/004119, filed on Feb. 5, 2019.Both of the priority documents are hereby incorporated by reference intheir entireties.

FIELD

The present invention relates to a method of the production of1,2-dichloro-3,3-difluoro-1-propene (hereinafter also referred to as1232xd) and a process of the co-production of 1232xd and1,2,3-trichloro-3-fluoro-1-propene (hereinafter also referred to as1231xd). The present invention also relates to a solvent compositioncomprising 1232xd, and a cleaning method of articles, a method forproducing a lubricant solution and an article with a lubricant coatingfilm, which use the solvent composition.

BACKGROUND

Hydrofluoroolefins (hereinafter also referred to as HFO) have a lowerglobal warming potential (GWP) than hydrochlorofluorocarbons (HCFCcompound) such as 1,3-dichloro-1,1,2,2,2-pentafluoropropane (225 ca),and are more Earth-environmentally friendly compounds, and so they arebeing replaced for various applications. 1232xd and 1231xd are alsotypes of HFO compounds.

Few methods for producing 1232xd and 1231xd are known, and it isdisclosed in “A. M. WHLEY and H. W. DAVIS J. Am. Chem. Soc., 1948, p.1026-1027” that 1232xd is obtained by reacting1,2,3,3-tetrachloro-1-propene (hereinafter also referred to as 1230xd)and 1 equivalent of antimony trifluoride at 100° C.

Since the reaction described in “A. M. WHLEY and H. W. DAVIS J. Am.Chem. Soc., 1948, p. 1026-1027” requires the same amount of antimonyfluoride, the environmental load is large, and there is room forimprovement in mass production.

Thus, it cannot be said that a method for producing 1232xd has beendeveloped sufficiently, and a more efficient method for producing 1232xdis required.

SUMMARY

The present invention has been made in view of the above. It is anobject of the present invention to provide an efficient method forproducing 1,2-dichloro-3,3-difluoro-1-propene (1232xd). It is an objectof the present invention to provide a solvent composition containing1232xd which is excellent in solubility of various organic substancesand is Earth-environmentally friendly, a method of cleaning articlesusing the solvent composition, a method of producing a lubricantsolution using the solvent composition, and a method of producing anarticle with a lubricant coating film.

As a result of intensive studies to solve the above-mentioned problems,the present inventors have found that the above-mentioned problems canbe solved and have completed the present invention. That is, the presentinvention includes the following inventions.

[Invention 1]

A method of producing 1,2-dichloro-3,3-difluoro-1-propene comprises astep of fluorinating 1,2,3,3-tetrachloro-1-propene with hydrogenfluoride.

[Invention 2]

The method according to the invention 1, wherein hydrogen fluoride isused at 2 mol or more and 40 mol or less for 1 mol of1,2,3,3-tetrachloro-1-propene.

[Invention 3]

The method according to the invention 1, wherein the fluorinating isperformed in a liquid phase.

[Invention 4]

The method according to the invention 3, wherein the fluorinating isperformed at a temperature of 100° C. or more and 200° C. or less.

[Invention 5]

The method according to the invention 1, wherein the fluorinating isperformed in a vapor phase.

[Invention 6]

The method according to the invention 5, wherein the fluorinating isperformed at a temperature of 100° C. or more and 500° C. or less.

[Invention 7]

The method according to any one of the inventions 1 to 6, wherein1,2,3-trichloro-3-fluoro-1-propene is produced together with1,2-dichloro-3,3-difluoro-1-propene by the fluorinating.

[Invention 8]

The method according to the invention 7, wherein the produced1,2,3-trichloro-3-fluoro-1-propene is provided for the fluorinating.

[Invention 9]

A method of producing 1,2-dichloro-3,3-difluoro-1-propene byfluorinating a composition includes 1,2,3,3-tetrachloro-1-propene and1,2,3-trichloro-3-fluoro-1-propene with hydrogen fluoride.

[Invention 10]

A method of producing both 1,2-dichloro-3,3-difluoro-1-propene and1,2,3-trichloro-3-fluoro-1-propene comprises a step of fluorinating1,2,3,3-tetrachloro-1-propene with hydrogen fluoride.

[Invention 11]

The method according to the invention 10, wherein the hydrogen fluorideis used at 2 mol or more and 40 mol or less for 1 mol of1,2,3,3-tetrachloro-1-propene.

[Invention 12]

The method according to the invention 10, wherein the fluorinating isperformed in a liquid phase.

[Invention 13]

The method according to the invention 12, wherein the fluorinating isperformed at a temperature of 100° C. or more and 200° C. or less.

[Invention 14]

The method according to the invention 10, wherein the fluorinating isperformed in a vapor phase.

[Invention 15]

The method according to the invention 14, wherein the fluorinating isperformed at a temperature of 100° C. or more and 500° C. or less.

[Invention 16]

A method according to any one of the inventions 1 to 15 comprises a stepof obtaining 1,2,3,3-tetrachloro-1-propene by contacting1,1,2,3,3-pentachloropropane with an aqueous solution of an inorganicbase in a liquid phase.

[Invention 17]

The method according to the invention 16 comprises a step of obtaining1,1,2,3,3-pentachloropropane by reacting 1,2-dichlroroethylene andchloroform under a presence of a Lewis acid catalyst.

[Invention 18]

The method according to the invention 17, wherein chloroform is used inan amount of more than 1 mol for 1 mol of 1,2-dichloroethylene.

[Invention 19]

A solvent composition comprises cis-1,2-dichloro-3,3-difluoro-1-propene.

[Invention 20]

A solvent composition comprises cis-1,2-dichloro-3,3-difluoro-1-propeneand trans-1,2-dichloro-3,3-difluoro-1-propene.

[Invention 21]

A solvent composition comprisestrans-1,2-dichloro-3,3-difluoro-1-propene.

[Invention 22]

The solvent composition according to any one of the inventions 19 to 21,further comprises 1,2,3-trichloro-3-fluoro-1-propene.

[Invention 23]

The solvent composition according to the inventions 19 to 22, furthercomprises at least one organic compound selected from a group consistingof hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, HFCsand HFEs.

[Invention 24]

The solvent composition according to any one of the inventions 19 to 23,further comprises at least one additive agent selected from a groupconsisting of a stabilizer, a surfactant, a flame retardant, a metalpassivator, and a corrosion inhibitor.

[Invention 25]

An aerosol composition comprises the solvent composition according toany one of the inventions 19 to 24, and injection gas.

[Invention 26]

A cleaning method of an article comprises a step of contacting thearticle with the solvent composition or the aerosol compositionaccording to any one of the inventions 19 to 25.

[Invention 27]

A method for producing a lubricant solution comprises obtaining thelubricant solution by diluting a lubricant agent with the solventcomposition or the aerosol composition according to any one of theinventions 19 to 25.

[Invention 28]

A method for producing an article with a lubricant, comprises coating alubricant solution including a lubricant agent and the solventcomposition or the aerosol composition according to any one of theinventions 19 to 25, and vaporizing the solvent composition or theaerosol composition from the article to form a coating film includingthe lubricant agent on a surface of the article.

[Invention 29]

A cleaning agent comprises the solvent composition or the aerosolcomposition according to any one of the inventions 19 to 25.

[Invention 30]

A draining agent comprises the solvent composition or the aerosolcomposition according to any one of the inventions 19 to 25.

[Invention 31]

A foaming agent comprises the solvent composition or the aerosolcomposition according to any one of the inventions 19 to 25.

[Invention 32]

A heat transfer medium comprises the solvent composition according toany one of the inventions 19 to 24.

[Invention 33]

An organic Rankine cycle system uses the heat transfer medium accordingto the invention 32.

[Invention 34]

A high-temperature heat pump cycle system uses the heat transfer mediumaccording to the invention 32.

[Invention 35]

A refrigeration cycle system uses the heat transfer medium according tothe invention 32.

[Invention 36]

A fire extinguishing composition comprises1,2-dichloro-3,3-difluoro-1-propene and at least nonflammable gas exceptfor 1,2-dichloro-3,3-difluoro-1-propene.

According to the present invention, an efficient method for theproduction of 1,2-dichloro-3,3-difluoro-1-propene (1232xd) can beprovided. Furthermore, according to the present invention, it ispossible to provide a solvent composition containing 1232xd which isexcellent in solubility of various organic substances and isEarth-environmentally friendly, a method of cleaning an article usingthe solvent composition, a method of producing a lubricant solutionusing the solvent composition, and a method of producing an article witha lubricant coating film.

DESCRIPTION OF EMBODIMENTS

(Description of Terms)

As used herein, unless otherwise specified, 1230xd means cis isomer,trans isomer, or a mixture thereof of 1,2,3,3-tetrachloro-1-propene.Unless otherwise specified, 1231xd means the cis isomer, the transisomer, or the mixture thereof of 1,2,3-trichloro-3-fluoro-1-propene.Unless otherwise specified, 1232xd means the cis isomer, the transisomer, or the mixture thereof of 1,2-dichloro-3,3-difluoro-1-propene.Unless otherwise specified, 1,2-dichloroethylene means the cis isomer,the trans isomer, or the mixture thereof.

In the present specification, “co-production of 1232xd and 1231xd” meansthat 1232xd and 1231xd are produced at least by the reaction accordingto the present invention, and preferably 1231xd is produced in an amountof 0.0001 mol or more, particularly preferably 0.001 mol or more per 1mol of 1232xd.

Hereinafter, the present invention will be described. The presentinvention is not limited to the following embodiments, and the presentinvention is also treated as encompassed by modifications andimprovements appropriately made to the following embodiments based onthe ordinary knowledge of a person skilled in the art without departingfrom the spirit of the present invention.

<Fluorination of 1,2,3,3-tetrachloro-1-propene (1230xd)>

In one embodiment of the present invention, 1230xd is fluorinated withhydrogen fluoride used as a fluorination agent. Thus, it is possible toproduce 1232xd.

In one embodiment, 1231xd can be produced by fluorination of 1230xd.

In one embodiment, 1230xd of fluorination can co-produce 1232xd and1231xd.

(1230xd)

1230xd is a known compound. A suitable example of the producing methodthereof will be described later, but this does not preclude adoption ofother producing methods.

In one embodiment of the present invention, 1231xd may be provided tofluorination with 1230xd in the fluorination of 1230xd for producing1232xd.

(Hydrogen Fluoride)

In the fluorination of 1230xd, the amount of hydrogen fluoride used isnot particularly limited as long as a target product can be obtained bythe fluorination of 1230xd. Normally, hydrogen fluoride is used in morethan a stoichiometric for 1 mol of 1230xd. The upper limit is notparticularly limited but is preferably 40 mol or less from the viewpointof economical production. The amount of hydrogen fluoride used isexpressed relative to the charge amount of 1230xd when the reaction typeis batch or semi-batch, and relative to the steady amount of 1230xdpresent in a reactor when the reaction type is continuous.

In one embodiment, to produce 1232xd advantageously, 3 mol or more and40 mol or less, preferably 4 mol or more and 30 mol or less, morepreferably 8 mol or more and 20 mol or less of hydrogen fluoride is usedper 1 mol of 1230xd.

In one embodiment, to advantageously produce 1231xd, 1 mol or more and20 mol or less, preferably 2 mol or more and 15 mol or less, morepreferably 4 mol or more and 10 mol or less of hydrogen fluoride is usedper 1 mol of 1230xd.

In one embodiment, to co-produce 1231xd and 1232xd dominantly, 2 mol ormore and 40 mol or less, preferably 3 mol or more and 30 mol or less,more preferably 4 mol or more and 20 mol or less, and still morepreferably 8 mol or more and 20 mol or less of hydrogen fluoride is usedper 1 mol of 1230xd.

<Fluorination of 1230xd in Liquid Phase>

In one embodiment, the fluorination of 1230xd by hydrogen fluoride canbe performed in a liquid phase.

The fluorination of 1230xd in the liquid phase may be performed in anyof batch, semi-continuous and continuous flow systems.

(Temperature)

In the fluorination of 1230xd in the liquid phase, the temperatures arenot particularly limited as long as the target product can be produced.The fluorination of 1230xd is usually carried out at 0° C. or more and200° C. or less, preferably 100° C. or more and 200° C. or less.

In one embodiment, since 1232xd can be advantageously produced, thefluorination of 1230xd is performed at 100° C. or more and 200° C. orless, preferably 110° C. or more and 200° C. or less, particularlypreferably 130° C. or more and 200° C. or less, more preferably 150° C.or more and 200° C. or less.

In one embodiment, when it is desired to predominantly produce 1231xd,the fluorination of 1230xd is carried out at 0° C. or more and 180° C.or less, preferably 20° C. or more and 150° C. or less, particularlypreferably 40° C. or more and 130° C. or less, and more preferably 60°C. or more and 130° C. or less.

In one embodiment, when 1232xd and 1231xd are co-produced, fluorinationof 1230xd is carried out at 0° C. or more and 200° C. or less,preferably 40° C. or more and 180° C. or less, particularly preferably80° C. or more and 180° C. or less, more preferably 100° C. or more and150° C. or less.

(Pressure)

In the fluorination of 1230xd in the liquid phase, the pressure is notparticularly limited as long as the target product can be produced.Generally, the fluorination of 1230xd in the liquid phase is carried outeither under normal pressure (under atmospheric pressure) or underpressure, preferably under pressure. In one embodiment of the presentinvention, the fluorination of 1230xd is carried out at 0.1 MPaG or moreand 10 MPaG or less (gauge pressure; the same shall apply herein),preferably at 1 MPaG or more and 6 MPaG or less, more preferably at 3MPaG or more and 6 MPaG or less. If the pressure is 0.1 MPaG or more,the reflux of unreacted hydrogen fluoride facilitates raising thereaction temperature to a suitable level, which is practical. If thepressure is 10 MPaG or less, the fluorination of 1230xd can be performedin a general-purpose reactor, which is economical. However, these do notpreclude the fluorination of 1230xd from being carried out at less than0.1 MPaG or greater than 10 MPaG.

(Solvent)

In the fluorination of 1230xd in the liquid phase, the use of a solventis not essential, and it is usually preferable not to use a solvent fromthe viewpoints of productivity and economics. On the other hand, the useof a solvent may be preferable from the viewpoints of homogeneity of thereaction and operability after the reaction. When a solvent is used, thetype of the solvent is not particularly limited as long as the 1230xdraw material can be dissolved, but an organic solvent that has a boilingpoint higher than that of the target product and that is not fluorinatedby hydrogen fluoride is preferable. Examples of such solvents includebut are not limited to tetramethylene sulfone (sulfolane),perfluoroalkanes, perfluoroalkenes, hydrofluorocarbons, and the like.The amount of the solvent used is not particularly limited as long asthe 1230xd raw material can be dissolved. For example, the amount of thesolvent used is preferably 80 mass % or less for the 1230xd raw material(when 1231xd is included in the raw material, the 1230xd raw materialmeans the total amount of 1230xd and 1231xd), and more preferably 40mass % or less, but more than these may be used as desired.

(Catalyst)

A catalyst may be used in the fluorination of 1230xd in the liquidphase. However, the use of the catalyst is not essential. When thecatalyst is used, the type of catalyst is, for example, Lewis acidcatalyst containing metal such as tin, titanium (more specifically, tinchloride (SnCl₄), titanium chloride (TiCl₄), etc.). The amount of thecatalyst used is, for example, 0.01 mol % or more and 20 mol % or lessper the 1230xd raw material.

(Reactor)

In the fluorination of 1230xd in the liquid phase, the material of thereactor to be used is preferably one that is inert to the raw materials,solvents, and the components of the reaction solution containing thereaction products and the like, and that is acid resistant. Suchmaterials include, for example, stainless steel (such as SUS304 andSUS316), Hastelloy™, Inconel™, Monel™, and the like. Such reactor iswell known in the art.

(Example of Operation Procedure)

An example of procedures for operating the fluorination of 1230xd in theliquid phase is provided below but is not limited thereto. In batchoperation or semi-continuous flow operation, for example, apredetermined amount of a predetermined raw material is introduced intothe reactor, a predetermined amount of a solvent is introduced asdesired, and a reaction is performed under predetermined conditions.When the catalyst is used, it is preferable to introduce the catalystinto the reactor in advance or together with a raw material or asolvent. The procedure for introducing the raw material into the reactoris not particularly limited. For example, 1230xd may be introduced intothe reactor, after which hydrogen fluoride may be introduced into thereactor. At this time, if a solvent is introduced as desired, a part orall of the solvent may be introduced into the reactor prior tointroducing hydrogen fluoride into the reactor, or may be introducedinto the reactor at the same time as introducing hydrogen fluoride, orhydrogen fluoride and the solvent may be mixed and introduced into thereactor.

In continuous-flow operation, for example, 1230xd and hydrogen fluorideare separately introduced in predetermined amounts into the reactor, andthe reaction is carried out under a predetermined condition. Optionally,the solvents used may be introduced into the reactor separately from the1230xd and hydrogen fluoride, or as a 1230xd solution and/or a hydrogenfluoride solution.

(Purification)

The method of purifying the target product from the reaction productobtained by the fluorination of 1230xd is not particularly limited, anda known purification method can be employed. If necessary, the reactionproducts can be rinsed with water, alkaline washing and the like toremove chlorine and acid components that can be contained in thereaction products. Moisture in the reaction product may also be removedby a dehydration treatment or the like or may be combined with atreatment for removing chlorine components and acid components.Furthermore, operations such as distillation may be performed.

Hereinafter, examples of methods for purifying 1232xd and 1231xd fromthe reaction product obtained by fluorination of 1230xd will bedescribed, but the present invention is not limited thereto. Forexample, high purity 1232xd or 1231xd can be obtained by flowing thereaction product through a cooled condenser to condense the reactionproduct, rinsing the reaction product with water or/and an alkalinesolution to remove chlorine components, acid components, and the likefrom the reaction product, drying the reaction product with a desiccantsuch as zeolite or activated carbon and carrying out a normaldistillation operation.

In one embodiment of the present invention, unreacted raw material1230xd or hydrogen fluoride may be recovered and used to thefluorination of 1230xd. In one embodiment, 1231xd produced byfluorination of 1230xd may be recovered and used to the fluorination of1230xd.

1232xd and 1231xd exist as a liquid at normal temperature and pressure.

Although the fluorination of 1230xd performed in the liquid phase hasbeen described above, in one embodiment, the fluorination of 1230xd byhydrogen fluoride may be performed in a vapor phase.

<Fluorination of 1230xd in the Vapor Phase>

(Catalyst)

The fluorination reaction of 1230xd in the vapor phase can be carriedout either in the presence or absence of a catalyst.

If the fluorination of 1230xd is carried out in the vapor phase in thepresence of the catalyst, a metal catalyst can be used. The metalcatalyst specifically includes at least one metal selected fromaluminum, vanadium, chromium, titanium, magnesium, manganese, iron,cobalt, nickel, copper, zirconium, niobium, molybdenum, ruthenium,rhodium, palladium, silver, tin, antimony, zinc, lanthanum, tantalum,and tungsten. As the metal catalyst, a compound of the above metal ispreferable, and an oxide, a halide, and an oxyhalide of the above metalare more preferable. The halogen of the halide may be any of iodine,bromine, chlorine, and fluorine. The metal catalyst is more preferablypartial halide or total halide of the above metal, and particularlypreferably partial fluoride or total fluoride of the above metal.

The metal catalyst may be a supported catalyst or an unsupportedcatalyst. The support of the supported catalyst is not particularlylimited, but carbon, an oxide of the aforementioned metal, an oxyhalide(preferably an oxyfluoride), a halide (preferably a fluoride), or thelike is preferably used. Among such supports, particularly preferred areactivated carbon, oxides of at least one metal selected from aluminum,chromium, zirconium and titanium, oxyhalides (particularly preferablyoxyfluorides), halides (particularly preferably fluorides). In the caseof the supported catalyst, the supported material supported on thesupport is a compound of the aforementioned metal. For example, a halide(e.g., fluoride, chloride, fluoride chloride) of the aforementionedmetal, an oxyhalide (e.g., oxyfluoride, oxychloride, oxyfluoridechloride), a nitrate, or the like is supported on the support. Such ametal compound may be supported alone, or two or more kinds may besupported together. Among the supported material, particularly preferredare halides and oxyhalides of at least one metal selected from aluminum,chromium, zirconium and titanium. Specific supported material includeschromium nitrate, chromium trichloride, potassium dichromate, titaniumtrichloride, manganese nitrate, manganese chloride, ferric chloride,nickel nitrate, nickel chloride, cobalt nitrate, cobalt chloride,antimony pentachloride, magnesium chloride, magnesium nitrate, zirconiumchloride, zirconium oxychloride, zirconium nitrate, copper(II) chloride,zinc(II) chloride, lanthanum nitrate, tin tetrachloride, and the like.In the case where the support and the supported material are metalcompounds, the support and the supported material are metal compoundsdifferent from each other.

The metallic catalyst is preferably used for the fluorination reactionof 1230xd after being subjected to fluorination treatment. Thefluorination treatment of the metal catalyst is not particularly limitedbut is generally carried out by contacting the metal catalyst with afluorination agent, such as hydrogen fluoride, fluorination hydrocarbon,or fluorination chlorinated hydrocarbon. The fluorination treatment isperformed at a temperature of 200° C. or more, for example, although thetemperature is not particularly limited. Although there is no particularupper limit to the fluorination treatment temperature, it is practicallypreferable to perform the treatment temperature at 600° C. or less. Inthis reaction, for example, Al₂O₃, Cr₂O₃, Cr₂O₃/Al₂O₃, Cr₂O₃/AlF₃,Cr₂O₃/C, Ti₂O₃, Zr₂O₃, Zr₂O₃/Ti₂O₃, CoCl₂/Cr₂O₃/Al₂O₃, NiCl₂/Cr₂O₃/Al₂O,CoCl₂/AlF₃, NiCl₂/AlF₃, FeCl₃/C, SnCl₄/C, TaCl₅/C, SbCl₃/C, AlCl₃/C, andAlF₃/C which are fluorinated can be used.

In one embodiment, when it is desired to predominantly produce 1231 xd,the fluorination of 1230xd is preferably carried out in the absence ofthe catalyst.

(Filler)

The fluorination reaction of 1230xd in the vapor phase may be carriedout in the presence or absence of fillers. Examples of the fillerinclude carbon such as activated carbon, heat-resistant plastic,ceramics, and zero-valent metal such as stainless steel and the like.Among these, activated carbon is particularly preferable. For example,the reaction can be carried out in the presence of at least a fillerselected from carbon, refractory plastics and ceramics.

(Temperature)

In the fluorination reaction of 1230xd in the vapor phase, the reactiontemperature is not particularly limited as long as the target productcan be produced. This reaction can be carried out at 100° C. or more,preferably at 170° C. or more, and more preferably at 220° C. or more.This reaction also can be carried out at 500° C. or less, preferably at480° C. or less, and more preferably at 430° C. or less. For example,the reaction can be performed at 100° C. or more and 500° C. or less,preferably 170° C. or more and 480° C. or less, and more preferably 220°C. or more and 430° C. or less.

(Pressure)

In the fluorination reaction of 1230xd in the vapor phase, the reactionpressure is not particularly limited. The reaction may be carried outunder reduced pressure, normal pressure (atmospheric pressure) or underpressure. This reaction can be carried out at a pressure of 0.01 MPaG ormore and 10 MPaG or less (meaning gauge pressure; the same shall applyhereinafter), and the reaction is preferably carried out at a pressureof 0.01 MPaG or more and 1 MPaG or less, and atmospheric pressure ismore preferable in order to prevent liquefaction of raw materials andproducts. Exceeding 10 MPaG is economically undesirable because itincreases the cost of the pressure resistance design of the reactor.

(Contact Time)

For the vapor phase flow reaction, productivity is often discussed asthe value (sec) obtained by dividing in which the volume A (mL) of thereaction zone by the feed rate B (mL/sec) of the raw material, which isreferred to as the contact time. When the reaction zone is equipped withthe catalyst, the apparent volume of the catalyst (mL) is considered tobe above A. The value of B indicates the “volume of material gasintroduced into the reactor per second”, in this case the value of B iscalculated from the number of moles of the material gas, pressure andtemperature, assuming that the material gas is an ideal gas. In thereactor, by-products of compounds other than raw materials and targetproducts and changes in the number of moles may occur but are not takeninto account when calculating the “contact time”.

The determination of the contact time depends on the raw materials usedin the reaction, the reaction temperature, the type of the catalyst, andthe like. Therefore, it is desirable to appropriately adjust the feedrate of the raw material for each of the raw material, the settemperature of the reactor, and the type of the catalyst to optimize thecontact time.

In the fluorination of 1230xd, the contacting time can be 0.1 seconds ormore and 300 seconds or less, preferably 5 seconds or more and 150seconds or less, more preferably 10 seconds or more and 100 seconds orless. The contact time may be appropriately changed in accordance withthe reaction pressure.

(Reactor)

In the fluorination reaction of 1230xd in the vapor phase, the reactoris not particularly limited, but it is preferable to use a reactorsuitable for the vapor phase reaction. The reactor is preferably formedof a material having heat resistance and acid resistance, and may beformed of, for example, stainless steel, Hastelloy™, Monel™, platinum,nickel, carbon, fluorine resin, or a material lined with thesematerials, but is not limited thereto.

In this reaction, inert gas such as nitrogen, argon, or helium, or anoxidizing gas such as chlorine, oxygen, or air may be supplied to thereactor in order to suppress a side reaction or to maintain or improvethe activity of the metal catalyst. Such gas may be supplied to thereactor alone or may be supplied to the reaction system together withthe reaction raw material. Such gas may be alone or mixed gas. The feedamount to the reactor is not particularly limited, but is preferably0.0001 mol % or more and 200 mol % or less, more preferably 0.001 mol %or more and 100 mol % or less, and particularly preferably 0.1 mol % ormore and 10 mol % or less with respect to the reaction material.

(Example of Operation Procedure)

An example of procedures of the fluorination reaction of 1230xd in thevapor phase is shown below. The reaction material is introduced into thereactor, and the vapor phase reaction is carried out under theabove-mentioned conditions. The raw material is preferably gaseous whenintroduced into the reactor, and if necessary, the raw material isgasified by a vaporizer and introduced into the reactor. When thecatalyst is used, it is preferable to equip the reactor with thecatalyst beforehand.

The method of purifying the target product from the reaction productobtained by this reaction is not particularly limited. If necessary,removal treatment of chlorine components, acid components, and the likewhich may be contained in the reaction product may be performed.Dehydration treatment or the like may be performed to remove moisture,or the dehydration treatment may be performed in combination with thetreatment to remove chlorine components or acid components. For example,the reaction product can be condensed by flowing through a cooledcondenser, rinsed with water or/and an alkaline solution to removechlorine components, acid components, and the like, dried with adesiccant such as zeolite, activated carbon, and the like, and thensubjected to a distillation operation to obtain an object of highpurity.

As explained above, the fluorination of 1230xd can be carried out notonly in the liquid phase but also in the vapor phase.

<Fluorination of 1231xd>

In one embodiment of the present invention, hydrogen fluoride is used asa fluorination agent to fluorinate 1231xd. Fluorination of 1231xd can bedone according to the above fluorination condition of 1230xd. Thus, itis possible to produce 1232xd.

In one embodiment, 1231xd may be produced by fluorination of 1230xd andthen 1232xd may be produced by fluorination of 1231xd.

<Producing Method of 1230xd>

[Dehydrochlorination Process of 240 da].

As described above, 1230xd is a known compound and can be produced byvarious methods, but by adopting the following 1230xd production method,1230xd can be produced efficiently using 1,1,2,3,3-pentachloropropane(hereinafter also referred to as 240 da) as a starting material.

1230xd can be produced in the liquid phase by a process ofdehydrochlorination of 240 da in the presence of an aqueous solution ofan inorganic base (hereinafter this process may be referred to as the“240 da dehydrochlorination process”).

(240 da)

240 da is a known compound and can be produced by various methods butcan be efficiently produced by the “alkylation process” described later.This does not preclude the production of 240 da by other methods.

(Aqueous Solution of Inorganic Base)

In the dehydrochlorination process of 240 da, there is no particularlimitation on an inorganic base as long as it can dehydrochlorination240 da. Specific examples include alkali metal hydroxides or alkalineearth metal hydroxides, and among these, at least one selected from thegroup consisting of lithium hydroxide, sodium hydroxide, potassiumhydroxide, magnesium hydroxide and calcium hydroxide is preferable.

The amount of the inorganic base used is not particularly limited.Generally, the amount is 1 equivalent or more to 240 da. The upper limitis not particularly limited, but is usually 10 equivalents or less,preferably 5 equivalents or less, more preferably 3 equivalents or less,and particularly preferably 2 equivalents.

The inorganic base concentration of the inorganic base in aqueoussolution is not particularly limited. Generally, the content is 5 mass %or more, preferably 10 mass %. The upper limit is not particularlylimited but is generally 40 mass % or less, preferably 30 mass %.

In one embodiment, the concentration of the inorganic base in aqueoussolution of the inorganic base is, for example, 5 mass % or more and 40mass % or less, 5 mass % or more and 30 mass % or less, 10 mass % ormore and 40 mass % or less, or 10 mass % or more and 30 mass % or less.

In one embodiment, the concentration of the inorganic base in aqueoussolution of the inorganic base is 5 mass % or more and 40 mass % orless, preferably 10 mass % or more and 30 mass % or less.

When a phase transfer catalyst described later is used, aqueous solutionof the inorganic base and the phase transfer catalyst may be supplied tothe reactor in separate streams but are preferably mixed in advance.

(Phase Transfer Catalyst)

The dehydrochlorination process of 240 da is preferably carried out inthe presence of the phase transfer catalyst. As such the phase transfercatalyst, water-soluble organic substances such as alcohols, ethers,ketones, amide compounds, and the like, or amine salts can be used.These phase transfer catalysts may be of one type or two or more types.

Examples of alcohols used as the phase transfer catalyst includealcohols having 1 to 4 carbon atoms.

The ethers used as the phase transfer catalyst include, for example,18-crown-6-ether and the like.

The ketones used as the phase transfer catalyst include, for example,acetone, ethyl methyl ketone, and the like.

Examples of amide compounds used as the phase transfer catalyst includeDMF, DMAc, and the like.

Examples of the amine salt used as the phase transfer catalyst includetetrabutylammonium salt, trioctylmethylammonium salt,benzyldimethyloctadecylammonium salt, and the like.

Among them, alcohols having 1 to 4 carbon atoms, 18-crown-6-ether,acetone, and ethyl methyl ketone are preferable as the phase transfercatalyst.

The amount of the phase transfer catalyst used is not particularlylimited as long as the effect as the phase transfer catalyst can beobtained. Generally, the amount of the phase transfer catalyst used withrespect to 240 da is 0.01 mass % or more, preferably 0.1 mass % or more.The upper limit is not particularly limited but is generally 40 mass %or less, preferably 20 mass % or less, more preferably 10 mass % orless.

In one embodiment, the amount of the phase transfer catalyst may be, forexample, 0.01 mass % or more and 40 mass % or less, 0.01 mass % or moreand 20 mass % or less, 0.01 mass % or more and 10 mass % or less, 0.01mass % or more and 0.1 mass % or less, 0.1 mass % or more and 40 mass %or less, 0.1 mass % or more and 20 mass % or less, or 0.1 mass % or moreand 10 mass % or less for 240 da.

In one embodiment, the amount of the phase transfer catalyst used is0.01 mass % or more and 40 mass % or less, preferably 0.1 mass % or moreand 20 mass % or less, for 240 da.

(Temperature)

In the 240 da dehydrochlorination process, the temperature is notparticularly limited as long as the target product can be produced undera liquid phase condition. Generally, it is carried out at 0° C. or more,preferably at 5° C. or more, more preferably at 10° C. or more. Theupper limit is not particularly limited, but is generally 150° C. orless, preferably 100° C. or less, more preferably 60° C. or less.

In one embodiment, the 240 da dehydrochlorination process is performed,for example, at 0° C. or more and 150° C. or less, 0° C. or more and100° C. or less, 0° C. or more and 60° C. or less, 5° C. or more and150° C. or less, 5° C. or more and 100° C. or less, 5° C. or more and60° C. or less, 10° C. or more and 150° C. or less, 10° C. or more and100° C. or less, 10° C. or more and 60° C. or less, 60° C. or more and150° C. or less, or 60° C. or more and 100° C. or less.

In one embodiment, the 240 da dehydrochlorination process is performedat 0° C. or more and 150° C. or less, preferably 5° C. or more and 100°C. or less, more preferably 10° C. or more and 60° C. or less.

(Pressure)

In the 240 da dehydrochlorination process, the pressure is notparticularly limited as long as the target product can be produced undera liquid phase condition. Generally, the pressure in the 240 dadehydrochlorination process is preferably equal to or higher thanatmospheric pressure and equal to or lower than 10 MPaG, and morepreferably equal to or higher than atmospheric pressure and equal to orlower than 1 MPaG. To reduce the cost of the reactor, the pressure inthe 240 da dehydrochlorination process is most preferably atmosphericpressure.

(Solvent)

In the dehydrochlorination process, the use of solvents is notessential. This does not prevent the dehydrochlorination process frombeing carried out in the presence of a solvent, but when a solvent isused, it is preferable to use a solvent which does not adversely affectthe reaction.

(Reaction Method)

The dehydrochlorination process may be performed by any of batch type,semi-continuous flow type, and continuous flow methods.

(Reactor)

In the dehydrochlorination process, the material of the reactor is notparticularly limited. A material having base resistance is preferable.Specifically, a reactor made of glass or stainless steel is preferable.A reactor lined with glass or resin is also preferred. Further, it ispreferable that the reactor is provided with various equipments such asa stirring equipment and a reflux tower.

In the case where the dehydrochlorination process and the alkylationprocess described later are performed in the same reactor, it ispreferable to provide an introduction pipe into which the liquid canflow.

(Example of Operation Procedure)

An example of the operating procedure of the dehydrochlorination processis described below but is not limited thereto. The phase transfercatalyst and 240 da are charged to a reactor equipped with a refluxcolumn through which a refrigerant (e.g., water) is flowed. An aqueoussolution of the inorganic base is flowed into a liquid inflow pipe, andthe reaction is carried out under a predetermined condition. Thereaction is terminated when it is observed that 240 da is nearlyconsumed by gas chromatographic analysis or the like of the sampledreactants.

(Purification)

The 1230xd obtained can be purified by a general purification operation.For example, raw materials and the like can be easily separated from1230xd by an operation such as distillation, preferably vacuumdistillation.

[Alkylation Process]

240 da can be efficiently produced by reacting 1,2-dichloroethylene withchloroform in the presence of Lewis acid catalyst (hereinafter thisprocess may be referred to as “alkylation process”).

(Raw Materials)

The amounts of 1,2-dichloroethylene and chloroform used in thealkylation process is not particularly limited as long as 240 da can beproduced. Generally, 1 mol or more of chloroform is used for 1 mol of1,2-dichloroethylene, or 1 mol of 1,2-dichloroethylene is used for 1 molof chloroform.

In one embodiment, chloroform is used in excess of stoichiometricamounts for 1,2-dichloroethylene. Thereby, by-products such asheptachloropentane can be suppressed. Specifically, chloroform is usedin an amount of more than 1 mol, preferably 2 mol or more, morepreferably 3 mol or more per 1 mol of 1,2-dichloroethylene. The upperlimit is not particularly limited, but chloroform is used in an amountof 20 mol or less, preferably 10 mol or less for 1 mol of1,2-dichloroethylene from the viewpoint of economical production.

In the alkylation process, heptachloropentane is a type of alkylatedcompound of 240 da, and by-products are produced as the existence ratioof 240 da in the reaction system increases. Therefore, in the reactionsystem, if chloroform as a raw material is present more than1,2-dichloroethylene, by-production of heptachloropentane can besuppressed.

(Lewis Acid Catalyst)

In the alkylation process, a metal halide can be used as Lewis acidcatalyst. Here, the metal halide refers to a compound having a bondbetween a metal atom and a halogen atom. The bonding of metalatoms-halogen atoms can be confirmed by infrared spectroscopy (IRmethod), X-ray diffraction method (XRD method), X-ray photoelectronspectroscopy (XPS method), etc. Specifically, such a metal halide ispreferably a metal halide of at least one metal selected from the groupconsisting of aluminum, vanadium, chromium, manganese, iron, cobalt,nickel, copper, zirconium, niobium, molybdenum, ruthenium, rhodium,palladium, silver, tin, antimony, tantalum, and tungsten. The metalhalide may be a fluoride, a chloride, a bromide, or an iodide of theabove metals, and among these, a chloride of the above metals ispreferable. In some embodiments, the chloride of at least one metalselected from the group consisting of aluminium, iron, tin and antimonyis particularly preferred as Lewis acid catalyst. Among these, aluminumchloride and iron chloride are more preferable, and ferric chloride ispreferable for iron chloride.

The use of anhydrous Lewis acid catalyst is preferred because it ishighly catalytically active. Commercial anhydrides of Lewis acidcatalyst may be used as is, or hydrates may be treated with adehydrating agent such as thionyl chloride to obtain anhydrides.

When a chloride of the above metal is used as Lewis acid catalyst,nitrate, carbonate, or the like of the above metal or a zero-valentmetal powder can be derived to the chloride of the metal byhydrochlorination in advance. Therefore, nitrate, carbonate, or the likeof the above metals, and zero-valent metal powders treated withhydrochloric acid can also be used as Lewis acid catalyst.

Since the chloroform raw material in the alkylation process is effectiveto activate and/or chlorinate the zero-valent metal, Lewis acid catalystmay be a zero-valent metal powder.

In the alkylation process, the amount of Lewis acid catalyst used is notparticularly limited as long as it is an effective amount as thecatalyst. The optimum amount varies depending on the type of catalystsand operating conditions such as the reaction temperatures, butgenerally, the amount of Lewis acid catalyst used is 0.01 mass % ormore, preferably 0.1 mass % or more for 1,2-dichloroethylene rawmaterial. The upper limit is not particularly limited but is generally40 mass % or less, preferably 20 mass % or less.

In one embodiment, the amount of Lewis acid catalyst used may be 0.01mass % or more and 40 mass % or less, 0.01 mass % or more and 20 mass %or less, 0.1 mass % or more and 40 mass % or less, or 0.1 mass % or moreand 20 mass % or less for 1,2-dichloroethylene.

In one embodiment, the amount of Lewis acid catalyst used is 0.01 mass %or more and 40 mass % or less, preferably 0.1 mass % or more and 20 mass% or less for 1,2-dichloroethylene. In this range, the reaction proceedsat a good reaction rate, and an unexpected side reaction is unlikely tooccur.

(Temperature)

In the alkylation process, temperature is not particularly limited aslong as the target product can be produced under a liquid phasecondition. Generally, it is carried out at 0° C. or more, preferably at20° C. or more, more preferably at 40° C. or more. The upper limit isnot particularly limited, but is generally 100° C. or less, preferably80° C. or less, more preferably 70° C. or less.

In one embodiment, the alkylation process is performed at temperature of0° C. or more and 100° C. or less, 0° C. or more and 80° C. or less, 0°C. or more and 70° C. or less, 20° C. or more and 100° C. or less, 20°C. or more and 80° C. or less, 20° C. or more and 70° C. or less, 40° C.or more and 100° C. or less, 40° C. or more and 80° C. or less, or 40°C. or more and 70° C. or less.

In some embodiments, the alkylation process is performed at 0° C. ormore and 100° C. or less, preferably 20° C. or more and 80° C. or less,more preferably 20° C. or more and 70° C. or less.

(Pressure)

In the alkylation process, the pressure is not particularly limited aslong as the target product can be produced under a liquid phasecondition. Generally, the alkylation process is performed at 0 MPaG ormore and 1 MPaG or less, preferably at 0 MPaG or more and 0.5 MPaG orless, and particularly preferably at atmospheric pressure.

(Solvent)

In the alkylation process, the use of a solvent is not essential. Thisdoes not prevent the alkylation process from being carried out in thepresence of a solvent, but in the case of using a solvent, it ispreferable to adopt a solvent which does not adversely affect thereaction.

(Reaction Method)

The alkylation process may be carried out in any method of a batch type,semi-continuous flow type, and continuous flow type. Since Lewis acidcatalyst is used in the alkylation process, it is preferable thatmoisture is as small as possible. In one embodiment, the water contentis preferably kept at 1 mass % or less, more preferably at 0.1 mass % orless for the total mass of the reaction material.

(Reactor)

In the alkylation process, the material of the reactor is notparticularly limited. A reactor made of glass or stainless steel ispreferred because chlorine gas or hydrogen chloride gas may bebyproducts, albeit in trace amounts. A reactor lined with glass or resinis also preferred. It is preferable that the reactor be provided withvarious equipments such as a liquid introducing pipe, a stirringequipment, and a reflux tower.

(Example of Operation Procedure)

An example of the operating procedure of the alkylation process isdescribed below but is not limited thereto. Lewis acid catalyst andchloroform are charged to a reactor equipped with a refluxing columnthrough which a coolant (e.g., water) is flowed. Seal with inert gas asnecessary. 1,2-dichloroethylene is flowed into the liquid inflow pipe,and the reaction is carried out under predetermined conditions. Thereaction is terminated when it is observed that 1,2-dichloroethylene isalmost consumed by gas chromatographic analysis or the like of thesampled reactants.

After completion of the reaction, acid aqueous solution is added to thereaction product. As the acidic aqueous solution, for example, aqueoussolution of at least one acid selected from the group consisting ofhydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide,formic acid, acetic acid, monofluoroacetic acid, difluoroacetic acid,trifluoroacetic acid, chlorodifluoroacetic acid, trichloroacetic acid,sulfuric acid, and nitric acid is used.

(Purification)

The resulting 240 da can be purified by conventional purificationprocedures. For example, raw materials and by-products can be easilyseparated from 240 da by operation such as distillation, preferablyvacuum distillation. The separated raw material may be reused as a rawmaterial for the alkylation process.

The obtained 240 da may be used as a raw material in the above-mentioneddehydrochlorination process without performing post-treatment such asseparating of Lewis acid catalyst and distilling purification. This doesnot preclude post-processing.

<Solvent Composition>

[1232xd]

The solvent composition of the present invention includes at least1232xd. The content of 1232xd is not particularly limited, but in oneembodiment, 1232xd is included in 20 mass % or more for the total amountof the solvent composition of the present invention. In anotherembodiment, 1232xd is included at 30 mass % or more for the total amountof the solvent composition of the present invention. In anotherembodiment, 1232xd is included in 40 mass % or more for the total amountof the solvent composition of the present invention. In yet anotherembodiment, 1232xd is included in an amount of 50 mass % or more for thetotal amount of the solvent composition of the present invention. In yetanother embodiment, 1232xd is included in an amount of 60 mass % or morefor the total amount of the solvent composition of the presentinvention. In yet another embodiment, 1232xd is included in an amount of70 mass % or more for the total amount of the solvent composition of thepresent invention. In yet another embodiment, 1232xd is included in anamount of 80 mass % or more for the total amount of the solventcomposition of the present invention. In yet another embodiment, 1232xdis included in an amount of 90 mass % or more for the total amount ofthe solvent composition of the present invention. In yet anotherembodiment, 1232xd is included an amount of 95 mass % or more for thetotal amount of the solvent composition of the present invention. In yetanother embodiment, 1232xd is included an amount of 97 mass % or morefor the total amount of solvent composition of the present invention. Inyet another embodiment, 1232xd is included 98 mass % or more for thetotal amount of the solvent composition of the present invention. In yetanother embodiment, 1232xd is included 99 mass % or more for the totalamount of the solvent composition of the present invention. In yetanother embodiment, the solvent composition of the present inventionconsists only of 1232xd.

In the solvent composition of the present invention, the content of1232xd may be 20 mass % or more and 99 mass % or less, 20 mass % or moreand 98 mass % or less, 20 mass % or more and 97 mass % or less, 20 mass% or more and 95 mass % or less, 20 mass % or more and 90 mass % orless, 20 mass % or more and 80 mass % or less, 20 mass % or more and 70mass % or less, 20 mass % or more and 60 mass % or less, 20 mass % ormore and 50 mass % or less, 20 mass % or more and 40 mass % or less, 20mass % or more and 30 mass % or less, 30 mass % or more and 99 mass % orless, 30 mass % or more and 98 mass % or less, 30 mass % or more and 97mass % or less, 30 mass % or more and 95 mass % or less, 30 mass % ormore and 90 mass % or less, 30 mass % or more and 80 mass % or less, 30mass % or more and 70 mass % or less, 30 mass % or more and 60 mass % orless, 30 mass % or more and 50 mass % or less, 30 mass % or more and 40mass % or less, 40 mass % or more and 99 mass % or less, 40 mass % ormore and 98 mass % or less, 40 mass % or more and 97 mass % or less, 40mass % or more and 95 mass % or less, 40 mass % or more and 90 mass % orless, 40 mass % or more and 80 mass % or less, 40 mass % or more and 70mass % or less, 40 mass % or more and 60 mass % or less, 40 mass % ormore and 50 mass % or less, 50 mass % or more and 99 mass % or less, 50mass % or more and 98 mass % or less, 50 mass % or more and 97 mass % orless, 50 mass % or more and 95 mass % or less, 50 mass % or more and 90mass % or less, 50 mass % or more and 80 mass % or less, 50 mass % ormore and 70 mass % or less, 50 mass % or more and 60 mass % or less, 60mass % or more and 99 mass % or less, 60 mass % or more and 98 mass % orless, 60 mass % or more and 97 mass % or less, 60 mass % or more and 95mass % or less, 60 mass % or more and 90 mass % or less, 60 mass % ormore and 80 mass % or less, 60 mass % or more and 70 mass % or less, 70mass % or more and 99 mass % or less, 70 mass % or more and 98 mass % orless, 70 mass % or more and 97 mass % or less, 70 mass % or more and 95mass % or less, 70 mass % or more and 90 mass % or less, 70 mass % ormore and 80 mass % or less, 80 mass % or more and 99 mass % or less, 80mass % or more and 98 mass % or less, 80 mass % or more and 97 mass % orless, 80 mass % or more and 95 mass % or less, 80 mass % or more and 90mass % or less, 90 mass % or more and 99 mass % or less, 90 mass % ormore and 98 mass % or less, 90 mass % or more and 97 mass % or less, 90mass % or more and 95 mass % or less, 95 mass % or more and 99 mass % orless, 95 mass % or more and 98 mass % or less, 95 mass % or more and 97mass % or less, 97 mass % or more and 99 mass % or less, 97 mass % ormore and 98 mass % or less, 98 mass % or more and 99 mass % or less, or100 mass %, for the total amount of the solvent composition of thepresent invention.

Since 1232xd is olefin having a double bond between carbon atoms, it hasa short lifetime in the air and a low global warming potential (GWP).Since 1232xd does not have a flash point, the risk of ignition and fireetc. in the use environment is low.

In one embodiment of the present invention, 1232xd consists only of thecis isomer (1232xd(Z)).

In another embodiment of the present invention, 1232xd consists of amixture of the cis isomer (1232xd(Z)) and the trans isomer (1232xd(E)).In the mixture of 1232xd(Z) and 1232xd(E), the composition is notparticularly limited, but may be the following molar ratio.

1232xd(Z):1232xd(E)=0.01˜99.99:99.99˜0.01

1232xd(Z):1232xd(E)=50.00˜99.99:50.00˜0.01

1232xd(Z):1232xd(E)=60.00˜99.99:40.00˜0.01

1232xd(Z):1232xd(E)=70.00˜99.99:30.00˜0.01

1232xd(Z):1232xd(E)=80.00˜99.99:20.00˜0.01

1232xd(Z):1232xd(E)=90.00˜99.99:10.00˜0.01

In yet another embodiment of the present invention, 1232xd consists onlyof the trans isomer (1232xd(E)).

[1231xd]

The solvent composition of the present invention may include 1231xdalong with 1232xd. In one embodiment, solvent composition containing1232xd and 1231xd has excellent cleaning performance. When the solventcomposition of the present invention contains 1231xd, the lower limit ofthe content thereof is 0.001 mass % or more in one embodiment, 0.01 mass% or more in another embodiment, 0.1 mass % or more in anotherembodiment, 1 mass % or more in another embodiment, 3 mass % or more inanother embodiment, 5 mass % or more in another embodiment, and 10 mass% or more in another embodiment, for the total amount of solventcomposition of the present invention. The upper limit of the content of1231xd is 40 mass % or less in one embodiment, 25 mass % or less inanother embodiment, and 15 mass % or less in another embodiment, for thetotal amount of the solvent composition of the present invention.

In the solvent composition of the present invention, the content of1231xd may be 0.001 mass % or more and 40 mass % or less, 0.001 mass %or more and 25 mass % or less, 0.001 mass % or more and 15 mass % orless, 0.001 mass % or more and 10 mass % or less, 0.001 mass % or moreand 5 mass % or less, 0.001 mass % or more and 3 mass % or less, 0.001mass % or more and 1 mass % or less, 0.001 mass % or more and 0.1 mass %or less, 0.001 mass % or more and 0.01 mass % or less, 0.01 mass % ormore and 40 mass % or less, 0.01 mass % or more and 25 mass % or less,0.01 mass % or more and 15 mass % or less, 0.01 mass % or more and 10mass % or less, 0.01 mass % or more and 5 mass % or less, 0.01 mass % ormore and 3 mass % or less, 0.01 mass % or more and 1 mass % or less,0.01 mass % or more and 0.1 mass % or less, 0.1 mass % or more and 40mass % or less, 0.1 mass % or more and 25 mass % or less, 0.1 mass % ormore and 15 mass % or less, 0.1 mass % or more and 10 mass % or less,0.1 mass % or more and 5 mass % or less, 0.1 mass % or more and 3 mass %or less, 0.1 mass % or more and 1 mass % or less, 1 mass % or more and40 mass % or less, 1 mass % or more and 25 mass % or less, 1 mass % ormore and 15 mass % or less, 1 mass % or more and 10 mass % or less, 1mass % or more and 5 mass % or less, 1 mass % or more and 3 mass % orless, 3 mass % or more and 40 mass % or less, 3 mass % or more and 25mass % or less, 3 mass % or more and 15 mass % or less, 3 mass % or moreand 10 mass % or less, 3 mass % or more and 5 mass % or less, 5 mass %or more and 40 mass % or less, 5 mass % or more and 25 mass % or less, 5mass % or more and 15 mass % or less, 5 mass % or more and 10 mass % orless, 10 mass % or more and 40 mass % or less, 10 mass % or more and 25mass % or less, 10 mass % or more and 15 mass % or less, 15 mass % ormore and 40 mass % or less, 15 mass % or more and 25 mass % or less, or25 mass % or more and 40 mass % or less, for the total amount of thesolvent composition of the present invention.

Since 1231xd is olefin having a double bond between carbon atoms, it hasa short lifetime in the air and a low global warming potential (GWP).Since 1231xd does not have a flash point, the risk of ignition and fireetc. in the use environment is low.

[Organic Compound (A)]

The solvent composition of the present invention may include anotherorganic compound (A) along with 1232xd or with 1232xd and 1231xd.

If the solvent composition of the present invention includes the organiccompound (A), the lower limit of the content, for the total amount ofthe solvent composition of the present invention, 0.01 mass % or more inone embodiment, 0.1 mass % or more in another embodiment, 1 mass % ormore in another embodiment, 3 mass % or more in another embodiment, 5mass % or more in another embodiment, 10 mass % or more in anotherembodiment. The upper limit of the content of the organic compound (A)is 80 mass % or less in one embodiment, 70 mass % or less in anotherembodiment, 60 mass % or less in another embodiment, 50 mass % or lessin another embodiment, 40 mass % or less in another embodiment, 30 mass% or less in another embodiment, and 20 mass % or less in anotherembodiment, for the total amount of the solvent composition of thepresent invention.

In the solvent composition of the present invention, the content of theorganic compound (A) may be 0.01 mass % or more and 80 mass % or less,0.01 mass % or more and 70 mass % or less, 0.01 mass % or more and 60mass % or less, 0.01 mass % or more and 50 mass % or less, 0.01 mass %or more and 40 mass % or less, 0.01 mass % or more and 30 mass % orless, 0.01 mass % or more and 20 mass % or less, 0.01 mass % or more and10 mass % or less, 0.01 mass % or more and 5 mass % or less, 0.01 mass %or more and 3 mass % or less, 0.01 mass % or more and 1 mass % or less,0.01 mass % or more and 0.1 mass % or less, 0.1 mass % or more and 80mass % or less, 0.1 mass % or more and 70 mass % or less, 0.1 mass % ormore and 60 mass % or less, 0.1 mass % or more 50 mass % or less, 0.1mass % or more and 40 mass % or less, 0.1 mass % or more and 30 mass %or less, 0.1 mass % or more and 20 mass % or less, 0.1 mass % or moreand 10 mass % or less, 0.1 mass % or more and 5 mass % or less, 0.1 mass% or more and 3 mass % or less, 0.1 mass % or more and 1 mass % or less,1 mass % or more and 80 mass % or less, 1 mass % or more and 70 mass %or less, 1 mass % or more and 60 mass % or less, 1 mass % or more and 50mass % or less, 1 mass % or more and 40 mass % or less, 1 mass % or moreand 30 mass % or less, 1 mass % or more and 20 mass % or less, 1 mass %or more and 10 mass % or less, 1 mass % or more and 5 mass % or less, 1mass % or more and 3 mass % or less, 3 mass % or more and 80 mass % orless, 3 mass % or more and 70 mass % or less, 3 mass % or more and 60mass % or less, 3 mass % or more and 50 mass % or less, 3 mass % or moreand 40 mass % or less, 3 mass % or more and 30 mass % or less, 3 mass %or more and 20 mass % or less, 3 mass % or more and 10 mass % or less, 3mass % or more and 5 mass % or less, 5 mass % or more and 80 mass % orless, 5 mass % or more and 70 mass % or less, 5 mass % or more and 60mass % or less, 5 mass % or more and 50 mass % or less, 5 mass % or moreand 40 mass % or less, 5 mass % or more and 30 mass % or less, 5 mass %or more and 20 mass % or less, 5 mass % or more and 10 mass % or less,10 mass % or more and 80 mass % or less, 10 mass % or more and 70 mass %or less, 10 mass % or more and 60 mass % or less, 10 mass % or more and50 mass % or less, 10 mass % or more and 40 mass % or less, 10 mass % ormore and 30 mass % or less, 10 mass % or more and 20 mass % or less, 20mass % or more and 80 mass % or less, 20 mass % or more and 70 mass % orless, 20 mass % or more and 60 mass % or less, 20 mass % or more and 50mass % or less, 20 mass % or more and 40 mass % or less, 20 mass % ormore and 30 mass % or less, 30 mass % or more and 80 mass % or less, 30mass % or more and 70 mass % or less, 30 mass % or more and 60 mass % orless, 30 mass % or more and 50 mass % or less, 30 mass % or more and 40mass % or less, 40 mass % or more and 80 mass % or less, 40 mass % ormore and 70 mass % or less, 40 mass % or more and 60 mass % or less, 40mass % or more and 50 mass % or less, 50 mass % or more and 80 mass % orless, 50 mass % or more and 70 mass % or less, 50 mass % or more and 60mass % or less, 60 mass % or more and 80 mass % or less, 60 mass % ormore and 70 mass % or less, or 70 mass % or more and 80 mass % or less,for the total amount of the solvent composition of the presentinvention.

Examples of the organic compound (A) include hydrocarbons, alcohols,ketones, ethers, esters, chlorocarbons, HFCs, HFEs, and the like. Theorganic compound (A) may be one kind or two or more kinds.

As the hydrocarbons used as the organic compound (A), hydrocarbonshaving 5 or more carbon atoms are preferable. The hydrocarbons may bechain, cyclic, saturated hydrocarbons, or unsaturated hydrocarbons.Specific examples of the hydrocarbons include n-pentane, 2-methylbutane,n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane,n-heptane, 2-methylhexane, 3-methylhexane, 2,4-dimethylpentane,n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane,2,2-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane,2-methl-3-ethylpentane, 3-methyl-3-ethylpentane, 2,3,3-trimethylpentane,2,3,4-trimethylpentane, 2,2,3-trimethylpentane, 2-methylheptane,2,2,4-trimethylpentane, n-nonane, 2,2,5-trimethylhexane, n-decane,n-dodecane, 2-methyl-2-butene, 1-pentene, 2-pentene, 1-hexene, 1-octene,1-nonene, 1-decene, cyclopentane, methylcyclopentane, cyclohexane,methylcyclohexane, ethylcyclohexane, bicyclohexane, cyclohexene,α-pinene, dipentene, decalin, tetralin, amylnaphthalene, and the like.Among these, n-pentane, cyclopentane, n-hexane, cyclohexane, andn-heptane are preferable.

As the alcohols used as the organic compound (A), alcohols having 1 to16 carbons are preferable. The alcohols may be chain, cyclic, saturatedalcohols, or unsaturated alcohols. Specific examples of the alcoholsinclude methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butylalcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol,1-pentanol, 2-pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol,3-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol,2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol,2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol,1-nonanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-undecanol,1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol,cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol,3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol,2,6-dimethyl-4-heptanol, nonyl alcohol, tetradecyl alcohol, and thelike. Among these, methanol, ethanol, n-propyl alcohol, and isopropylalcohol are preferable.

As the ketones used as the organic compound (A), ketones having 3 to 9carbon atoms are preferable. The ketones may be chain, cyclic, saturatedketones or unsaturated ketones. The ketones include acetone, methylethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutylketone, 2-heptanone, 3-heptanone, 4-heptanone, diisobutyl ketone,mesityl oxide, phorone, 2-octanone, cyclohexanone, methylcyclohexanone,isophorone, 2,4-pentanedione, 2,5-hexanedione, diacetone alcohol,acetophenone, and the like. Among them, acetone and methyl ethyl ketoneare preferable.

As the ethers used as the organic compound (A), ethers having 2 to 8carbons are preferable. The ethers may be chain, cyclic, saturatedethers, or unsaturated ethers. Specific examples of the ethers includediethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, ethylvinyl ether, butyl vinyl ether, anisole, phenetole, methyl anisole,furan, methyl furan, tetrahydrofuran, and the like. Among these, diethylether, diisopropyl ether and tetrahydrofuran are preferable.

As the esters used as the organic compound (A), esters having 2 to 19carbons are preferable. The esters may be chain, cyclic, saturatedesters, or unsaturated esters. Specific examples of the esters includemethyl formate, ethyl formate, propyl formate, butyl formate, isobutylformate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate,isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate,pentyl acetate, methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutylacetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate,methyl propionate, ethyl propionate, butyl propionate, methyl butyrate,ethyl butyrate, butyl butyrate, isobutyl butyrate,2-hydroxy-2-methylpropionic acid ethyl, methyl benzoate, ethyl benzoate,propyl benzoate, butyl benzoate, benzyl benzoate, γ-butyrolactone,diethyl oxalate, dibutyl oxalate, dipentyl oxalate, diethyl malonate,dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl tartrate,tributyl citrate, dibutyl sebacate, dimethyl phthalate, diethylphthalate, and dibutyl phthalate. Among them, methyl acetate and ethylacetate are preferable.

As the chlorocarbons used as the organic compound (A), chlorocarbonshaving 1 to 3 carbon atoms are preferable. The chlorocarbons may bechain, cyclic, saturated chlorocarbons, or unsaturated chlorocarbons.Specific examples of chlorocarbons include methylene chloride,1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane,1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane,1,1-dichloroethylene, cis-1,2-dichloroethylene,trans-1,2-dichloroethylene, trichloroethylene, tetrachloroethylene,1,2-dichloropropane, and the like. Among these, methylene chloride,trans-1,2-dichloroethylene, and trichloroethylene are more preferable.

As the HFCs used as the organic compound (A), chained or cyclic HFCshaving 4 to 8 carbons are preferable, and the HFCs having fluorine atomsin one molecule equal to or more than hydrogen atoms are morepreferable. Specific examples of the HFCs include1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane,1,1,2,2,3,3,4-heptafluorocyclopentane,1,1,1,2,2,3,3,4,4-nonafluorohexane,1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane,1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, and the like. Amongthese, 1,1,1,2,2,3,4,5,5,5-decafluoropentane,1,1,1,2,2,3,3,4,4-nonafluorohexane,1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane are preferable.

As the HFEs used as the organic compound (A), C₄F₉OCH₃, C₃F₇OCH₃,1,1,2,2-tetrafluoroethoxy-1-(2,2,2-trifluoro) ethane (HFE-347pc-f), andthe like are preferable.

In one embodiment, it is further preferred that the organic compound (A)is a compound that does not have a flash point. Examples of compoundsthat do not have a flash point include HFCs such as1,1,1,2,2,3,4,5,5,5-decafluoropentane,1,1,1,2,2,3,3,4,4-nonafluorohexane,1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, and HFEs such as1,1,2,2-tetrafluoroethoxy-1-(2,2,2-trifluoro)ethane. When a compoundhaving a flash point is used as the organic compound (A), it ispreferable to use the compound so as not to have a flash point as thesolvent composition of the present invention.

[Additive Agent (B)]

The solvent composition of the present invention may contain an additiveagent (B) to the extent that the effects of the present invention arenot impaired. In one embodiment, the additive agent (B) is included in0.0001 mass % or more, in another embodiment in 0.001 mass % or more, inanother embodiment in 0.01 mass % or more, in another embodiment in 0.1mass % or more, in another embodiment in 1 mass % or more, and inanother embodiment in 3 mass % or more, for the total amount of thesolvent composition of the present invention. In one embodiment, theadditive agent (B) is included in 10 mass % or less, in anotherembodiment, in 5 mass % or less, in another embodiment, in 3 mass % orless, in another embodiment, in 1 mass % or less, in another embodiment,in 0.1 mass % or less, in another embodiment, in 0.01 mass % or less,and in another embodiment, in 0.001 mass % or less for the total amountof the solvent composition of the present invention.

In the solvent composition of the present invention, the content of theadditive agent (B) may be 0.0001 mass % or more and 10 mass % or less,0.0001 mass % or more and 5 mass % or less, 0.0001 mass % or more and 3mass % or less, 0.0001 mass % or more and 1 mass % or less, 0.0001 mass% or more and 0.1 mass % or less, 0.0001 mass % or more and 0.01 mass %or less, 0.0001 mass % or more and 0.001 mass % or less, 0.001 mass % ormore and 10 mass % or less, 0.001 mass % or more and 5 mass % or less,0.001 mass % or more and 3 mass % or less, 0.001 mass % or more and 1mass % or less, 0.001 mass % or more and 0.1 mass % or less, 0.001 mass% or more and 0.01 mass % or less, 0.01 mass % or more and 10 mass % orless, 0.01 mass % or more and 5 mass % or less, 0.01 mass % or more and3 mass % or less, 0.01 mass % more and 1 mass % or less, 0.01 mass % ormore and 0.1 mass % or less, 0.1 mass % or more and 10 mass % or less,0.1 mass % or more and 5 mass % or less, 0.1 mass % or more and 3 mass %or less, 0.1 mass % or more and 1 mass % or less, 1 mass % or more and10 mass % or less, 1 mass % or more and 5 mass % or less, 1 mass % ormore and 3 mass % or less, 3 mass % or more and 10 mass % or less, 3mass % or more and 5 mass % or less, 5 mass % or more and 10 mass % orless for the total amount of the solvent composition of the presentinvention.

Examples of the additive agent (B) include a stabilizer, a surfactant, aflame retardant, a metal-passivating agent, and a corrosion-inhibitorand the like. It is preferable that these additive agents (B) areappropriately selected in accordance with various applications of thesolvent composition of the present invention.

(Stabilizer)

In one embodiment, the solvent composition of the present invention maycontain a stabilizer to inhibit degradation of the composition evenunder harsh conditions, such as heat conditions. Examples of suchstabilizers include nitro compounds, epoxy compounds, phenols,imidazoles, amines, phosphorus compounds, sulfur compounds,nitrogen-containing alcohol compounds, diene-based compounds, aromaticunsaturated hydrocarbons, isoprenes, propadienes, terpenes, and thelike. The stabilizer may be one kind or two or more kinds.

Specific examples of nitro compounds used as the stabilizer includealiphatic nitro compounds such as nitromethane, nitroethane,1-nitropropane, 2-nitropropane, etc., and aromatic nitro compounds suchas nitrobenzene, o-, m- or p-dinitrobenzene, trinitrobenzene, o-, m- orp-nitrotoluene, o-, m- or p-ethylnitrobenzene, 2,3-, 2,4-, 2,5-, 2,6-,3,4- or 3,5-dimethylnitrobenzene, o-, m- or p-nitroacetophenone, o-, m-or p-nitrophenol, o-, m- or p-nitroanisole.

Specific examples of the epoxy compound used as the stabilizer includemonoepoxy compounds such as ethylene oxide, 1,2-butylene oxide,propylene oxide, styrene oxide, cyclohexene oxide, glycidol,epichlorohydrin, glycidyl methacrylate, phenylglycidyl ether,allylglycidyl ether, methylglycidyl ether, butylglycidyl ether,2-ethylhexylglycidyl ether, and the like, and polyepoxy compounds suchas diepoxybutane, vinylcyclohexenedioxide, neopentylglycol diglycidylether, ethylene glycol diglycidyl ether, glycerun polyglycidyl ether,trimethylolpropane triglycidyl ether, and the like.

The phenolic used as the stabilizer may have a substituent such as analkyl group, an alkenyl group, an alkoxy group, a carboxyl group, acarbonyl group, halogen and the like in addition to a hydroxyl group.Specific examples of the phenols include univalent phenols such as2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, p-t-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, eugenol,isoeugenol, butylated hydroxyanisole, phenol, xylenol, etc. and divalentphenols such as t-butyl catechol, hydroquinone, methylhydroquinone,t-butylhydroquinone, 2,5-di-t-amylhydroquinone,2,5-di-t-butylhydroquinone, 2,2′-methylene-bis(4-methyl-6-t-butylphenol)and 2,2′-methylene-bis (4-ethyl-6-t-butylphenol) and the like.

Imidazoles used as the stabilizer, imidazoles having a hydrocarbon grouphaving 1 to 18 carbon atoms as a substituent at the N position arepreferable. The hydrocarbon group may be chain, cyclic, and may be asaturated hydrocarbon group, or may be an unsaturated hydrocarbon group.Examples of imidazoles include 1-methylimidazole, 1-n-butylimidazole,1-phenylimidazole, 1-benzylimidazole, 1-(β-oxyethyl)imidazole,1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole,1-n-butyl-2-methylimidazole, 1,2-dimethylimidazole,1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole,1,4,5-trimethylimidazole, 1-ethyl-2-methylimidasole,2-mercaptobenzimidazole, and the like.

Specific examples of amines used as the stabilizer include pentylamine,hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine,diallylamine, triethylamine, N-methylaniline, pyridine, morpholine,N-methylmorpholine, triallylamine, allylamine, α-methylbenzylamine,methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine,propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine,dibutylamine, tributylamine, dibenzylamine, tribenzylamine,2-ethylhexylamine, aniline, N,N-dimethylaniline, N,N-diethylaniline,ethylenediamine, propylenediamine, diethylenetriamine,tetraethylenepentamine, benzylamine, diphenylamine,diethylhydroxylamine, diphenylamine, 4-aminodiphenylamine,N-phenyl-1-naphthylamine, phenothiazine, and the like.

Specific examples of phosphorus compounds used as the stabilizer includetriphenyl phosphite, isodecyl diphenyl phosphite, phenyldiisodecylphosphite, tris(nonylphenyl)phosphite, andtris(2,4-di-t-butylphenyl)phosphite and the like.

Specific examples of sulfur compounds used as the stabilizer include3,3′-thiodipropionate didodecyl, 3,3′-thiodipropionate ditetradecyl,3-(dodecylthio)propionic acid, 3,3′-thiodipropionate dioctadecyl, andthe like.

Specific examples of nitrogen-containing alcohol compounds used as thestabilizer includeN-stearyl-N,N′,N′-tris(polyoxyethylene)-1,3-diaminopropane,ethylenediamine-N,N′-diethanol,ethylenediamine-N,N,N′,N′-tetra-2-propanol,triethylenetetramine-N-2-propanol, xylenediamine-N-2-propanol,alkylolamide, oleic acid triethanolamine ester,laurylamine-N,N-diethanol, stearylamine-N,N-diethanol,oleylamine-N,N-diethanol, bis(2-hydroxyethyl) soyamine, oleic aciddialcohol amide, stearyl aminopropyl amino ethanol,1,3-propylenediamine-N—C₁₂₋₁₈-alkyl-N′-ethanol and the like.

Specific examples of the aromatic unsaturated hydrocarbons used as thestabilizer include α-methylstyrene, p-isopropenyltoluene and the like.

(Surfactants)

In one embodiment, the solvent composition of the present invention canfurther improve detergency, interfacial action, etc. by including asurfactant. Such surfactants include cationic surfactants, nonionicsurfactants, anionic surfactants, amphoteric surfactants and the like.The surfactant may be one kind or two or more kinds.

Examples of preferred cationic surfactants include quaternary ammoniumsalts such as dodecyldimethylammonium chloride, trimethylammoniumchloride, and the like. Examples of preferable nonionic surfactantsinclude surfactants such as polyoxyalkylene nonylphenyl ether,polyoxyalkylene alkyl ether, fatty acid alkanolamide, glycerol fattyacid ester, sorbitan fatty acid ester, sucrose fatty acid ester,propylene glycol fatty acid ester, esters of phosphoric acid and fattyacid and the like. Examples of preferred anionic surfactants includealkyl sulfate ester salts such as polyoxyethylene alkyl sulfate salts,and the like, carboxylates such as fatty acid salts (soaps), and thelike, sulfonates such as α-olefin sulfonates, lauryl sulfate, and thelike. Examples of preferred amphoteric surfactants include betainecompounds such as alkyl betaines and the like.

(Flame Retardants)

In one embodiment, the solvent composition of the present invention mayinclude a flame retardant to improve non-flammability. Examples of suchflame retardants include phosphates, halogenated aromatic compounds,fluorinated iodocarbons, fluorinated bromocarbons, and the like.

[Other Components]

The solvent composition of the present invention may contain othercomponents as long as the effects of the present invention are notimpaired. The other components are not particularly limited as long asthey are other than the above-mentioned components, that is, 1232xd,1231xd, the organic compound (A), and the additive agent (B). Forexample, impurities derived from the above-mentioned components may becontained. Examples of such impurities include, but are not limited to,the raw materials used in the manufacturing process of theabove-mentioned components.

<Cleaning Agent>

The solvent composition of the present invention has adequate fluidityand solubility and is therefore suitable for flushing and dissolving toremove foreign matter from articles.

Materials for the article include metals, resins, rubbers, fibers,glasses, ceramics, and composites thereof. Examples of compositesinclude a laminate of metals and resins, and the like. Specific examplesof the articles include, but are not limited to, precision mechanicalcomponents, electronic materials (such as print substrate, liquidcrystal displays, magnetic recording components, semiconductormaterials, etc.), resinous processed components, optical lenses,textiles, medical instruments, and the like.

Examples of the foreign matter include, but are not limited to, grease,processing oil, silicone oil, fat, flux, wax, ink, mineral oil, arelease agent including silicone oil, and the like, dust, liquiddroplets, water droplets, and the like.

In the cleaning of various vehicles, vehicles, and transportation suchas automobiles, motorcycles, bicycles, construction machinery,agricultural machinery, aircraft, railway vehicles, and marine vessels(in particular, the brake cleaning thereof), the process of wetting andrinsing off the dirt is required. The composition of the presentinvention is suitable for such cleaning because it has an appropriateboiling point and can wet and rinse off the dirt.

The cleaning process of the article is not particularly limited, but thearticle is contacted with the solvent composition of the presentinvention or an aerosol composition described below. For example, thearticle to be cleaned may be immersed in the solvent composition of thepresent invention to rinse off the dirt, wiped off the dirt with a wastecloth, spray-cleaned, and the like, and combinations thereof may beused. It is a particularly preferable embodiment to place the solventcomposition in an ultrasonic cleaning machine, immerse the article to becleaned in the liquid, and carry out ultrasonic cleaning treatment.Also, spray cleaning, e.g., the method, in which the solvent compositionof the present invention is mixed with an injection gas, the mixture isaerosolized and the aerosolized mixture is splayed to the variousarticles, is also one of the preferred embodiments.

<Aerosol Composition>

The inventive solvent composition may be mixed with the injection gas toform an aerosol composition.

As the injection gas, liquefied gas or compressed gas can be used.Examples include, but are not limited to, gases, such as LPG (liquefiedpetroleum gas), DME (dimethyl ether), carbon dioxide, chlorofluorocarbongas, nitrogen gas, compressed air, and the like, a combination of two ormore of the above gases, such as a mixture of LPG and DME, a mixture ofLPG and carbon dioxide, and the like.

The aerosol composition of the present invention can be produced bymixing the solvent composition of the present invention and theabove-mentioned injection gas and can be provided with filling apressure-resistant can.

<For Dry-Cleaning>

The solvent composition of the present invention is suitable as acleaning agent for textiles, i.e. as a dry-cleaning agent. Textileproducts include clothing such as shirts, sweaters, jackets, skirts,trousers, jumpers, gloves, mufflers, stools, and the like. The solventcomposition of the present invention is particularly suitable fordry-cleaning of textiles comprising acrylic fibers.

The process of dry-cleaning a textile using the solvent composition ofthe present invention includes removing soils adhering to the textilesurface by contacting the composition with the textile surface. In thiscase, it is preferable to use the aforementioned surfactant as theadditive agent in the composition of the present invention.

<Diluted Solution>

The solvent composition of the present invention or the aerosolcomposition is suitable as a diluent for diluting various chemicals. Inone embodiment of the diluent, the solvent composition of the presentinvention can be mixed with a lubricant to form a lubricant solution.

<Producing Method of Dilute Solution>

Various chemicals that can be diluted by the solvent composition or theaerosol composition of the present invention are not particularlylimited, and include, for example, lubricants and rust-preventiveagents.

As an embodiment of the method for producing the dilute solution, amethod for producing a lubricant solution will be described below. Thelubricant solution can be produced by diluting a lubricant with thesolvent composition of the present invention. By applying the lubricantsolution to the surface of an article and then volatilizing the solventcomposition of the present invention from the article, a coated articlecan be produced in which a coating comprising the lubricant is formed onthe surface of the article. The lubricant solution of the presentinvention can be applied without affecting the article containingresinous materials.

Methods of applying the lubricant solution include, for example, brushapplication, spraying application, application by immersing the articlein the lubricant solution, and application by contacting the inner wallof tubes or needles with the lubricant solution by wicking the lubricantsolution.

The lubricant is used to reduce friction on the contact surface and toprevent heat generation and wear damage when two members move in contactwith each other. The lubricant may be in the form of liquids (oils),semi-solids (greases), or solids. The lubricant is preferably a mineraloil-based lubricant, a synthetic oil-based lubricant, a fluorine-basedlubricant, or a silicone-based lubricant from the viewpoint of excellentsolubility in the compositions of the present invention. Thefluorine-based lubricant is meant a lubricant having fluorine atoms inits molecules. The silicone-based lubricant is meant a lubricantcomprising silicone. The lubricant contained in the lubricant solutionmay be one kind or two or more kinds. Each of fluorine-based lubricantand silicone-based lubricant may be used alone or in combination.

Examples of the fluorine-based lubricant include fluorine oil, fluorinegrease, fluorine-based solids lubricant such as polytetrafluoroethylenepowder, and the like. As the fluorine oil, a low polymer ofperfluoropolyether or chlorotrifluoroethylene is preferable. Forexample, the product names “Krytox® GPL102” (manufactured by DuPont deNemours, Inc.), “Dyfloil #1”, “Dyfloil #3”, “Dyfloil #10”, “Dyfloil#20”, “Dyfloil #50”, “Dyfloil #100”, and “Demnam S-65” (manufactured byDAIKIN INDUSTRIES, LTD), and the like are included. As the fluorinegrease, fluorine oil such as perfluoropolyether or low polymer ofchlorotrifluoroethylene is preferably used as a base oil, andpolytetrafluoroethylene powder or other thickener is preferably mixed.For example, the product names “Krytox® Grease 240AC” (manufactured byDuPont de Nemours, Inc.), “DAIFLOIL GREASE DG-203”, “Demnam L65”,“Demnam L100”, “Demnam L200” (manufactured by DAIKIN INDUSTRIES, LTD),“Smitech F936” (manufactured by Sumitomo Lubricant Co., Ltd.),“MOLYKOTE® HP-300”, “MOLYKOTE® HP-500”, “MOLYKOTE® HP-870”, “MOLYKOTE®6169”, and the like are included.

Examples of the silicone-based lubricant include silicone oil andsilicone grease. As the silicone oil, dimethyl silicone, methyl hydrogensilicone, methylphenyl silicone, cyclic dimethyl silicone, and modifiedsilicone oil in which an organic group is introduced to a side chain ora terminal thereof is preferable. Examples include the product names“Shin-Etsu Silicone KF-96”, “Shin-Etsu Silicone KF-965”, “Shin-EtsuSilicone KF-968”, “Shin-Etsu Silicone KF-868”, “Shin-Etsu SiliconeKF-99”, “Shin-Etsu Silicone KF-50”, “Shin-Etsu Silicone KF-54”,“Shin-Etsu Silicone HIVACF-4”, “Shin-Etsu Silicone HIVACF-5”, “Shin-EtsuSilicone KF-56A”, “Shin-Etsu Silicone KF-995” (manufactured by Shin-EtsuChemical Co., Ltd.), “SH200”, and “MDX4-4159” (manufactured by Toray DowCorning Co., Ltd.) and the like. As the silicone grease, products inwhich various silicone oils listed above are used as base oils,thickeners such as metallic soap, and various additive agent are blendedare preferable. For example, products names “Shin-Etsu Silicone G-30Series”, “Shin-Etsu Silicone G-40 Series”, “Shin-Etsu Silicone FG-720Series”, “Shin-Etsu Silicone G-411”, “Shin-Etsu Silicone G-501”,“Shin-Etsu Silicone G-6500”, “Shin-Etsu Silicone G-330”, “Shin-EtsuSilicone G-340”, “Shin-Etsu Silicone G-350”, “Shin-Etsu Silicone G-630”(manufactured by Shin-Etsu Chemical Co., Ltd.), “MOLYKOTE® SH33L”,“MOLYKOTE® 41”, “MOLYKOTE® 44”, “MOLYKOTE® 822M”, “MOLYKOTE® 111”,“MOLYKOTE® High-Vacuum Grease”, “MOLYKOTE® heat transferable compound”,(manufactured by Toray Dow Corning Co., Ltd.) and the like.

The content of the lubricant in the lubricant solution of the presentinvention is preferably 0.01 mass % or more and 50 mass % or less, morepreferably 0.05 mass % or more and 30 mass % or less, and still morepreferably 0.1 mass % or more and 20 mass % or less, for the totalamount of the lubricant solution. If the content of the lubricant iswithin the above range, it is easy to adjust the thickness of thecoating film when the lubricant solution is applied and the thickness ofthe dried lubricant coating film to an appropriate range.

<Draining Agent Use>

In one embodiment, the solvent composition of the present invention orthe aerosol composition can be used as a draining agent.

<Foaming Agent Use>

The solvent composition of the present invention or the aerosolcomposition can be used as a foaming agent for the production of rigidpolyurethane foams or polyisocyanurate foams. That is, rigidpolyurethane or polyisocyanurate foams can be produced by reacting apremix of foaming agent comprising the solvent composition or theaerosol composition of the present invention, one or more polyols,catalysts, foam stabilizers, and the like with isocyanates.

The isocyanates include those of aromatic, cyclic aliphatic, chainaliphatic, and the like, and generally bifunctional ones are used. Suchisocyanates include, for example, polyisocyanates such as tolylenediisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylpolyisocyanate, tolylene diisocyanate, naphthalene diisocyanate,hexamethylene diisocyanate, isophorone diisocyanate, xylylenediisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethaneisocyanate and the like, as well as pre-polymeric, nulate, and ureamodifications thereof. They may be used alone or in a mixture.

The polyols included in the premix include polyether-based polyols,polyester-based polyols, polyhydric alcohols, hydroxyl group-containingdiethylene-based polymers, and the like, but polyether-based polyols aregenerally used. Also, polyester polyols and polyether polyols may be themain components, and other polyols may be used.

Examples of the polyester polyol include phthalic anhydride, wastepolyester, and compounds derived from castor oil as well as acondensation polyester polyol, a lactone polyester polyol, and apolycarbonate polyol and the like.

From the viewpoints of compatibility with foaming agent, foamingproperty, foam physical properties, and the like, it is preferable thatthe hydroxyl value (OH value) of the polyester polyol is 100 mg KOH/g ormore and 400 mg KOH/g or less, and the viscosity is 200 mPa·s/25° C. ormore and 4000 mPa·s/25° C. or less.

As the polyether polyol, polypropylene glycol, polytetramethyleneglycol, and modified forms thereof as well as compounds obtained byadding a cyclic ether such as propylene oxide, ethylene oxide,epichlorohydrin, butylene oxide and the like to a initiator of acompound containing active hydrogen such as sugars, polyhydric alcohols,alkanolamines, and the like are preferably used.

As the polyether polyol, one having a hydroxyl value of 400 mg KOH/g ormore and 1000 mg KOH/g or less is usually used.

The catalyst included in the premix includes an organometallic catalystand an organoamine catalyst. As the organometallic catalyst, anorganotin compound is preferably used, and stanas octoate, stanaslaurate, dibutyltin dilaurate, dibutyltin dimalate, dibutyltindiacetate, dioctyltin diacetate, and the like can be cited. Theorganoamine catalyst include tertiary amines such as triethylenediamine,N-ethylmorpholine, bis(2-dimethylaminoethyl) ether,N,N′,N′-triethylethanolamine, and the like.

As the foam stabilizer included in the premix, an organosiliconcompound-based surfactant is usually used, and SH-193, SH-195, SH-200 orSRX-253 and the like manufactured by Toray Silicone Co., Ltd., F-230,F-305, F-341, F-348 and the like manufactured by Shin-Etsu Silicone Co.,Ltd., L-544, L-5310, L-5320, L-5420, L-5720 manufactured by NipponUnicar Co., Ltd., and TFA-4200, TFA-4202 and the like manufactured byToshiba Silicone Co., Ltd. can be cited.

Flame retardants included in the premix include tris(2-chloroethyl)phosphate, tris(2-chloropropyl) phosphate, tris(butoxyethyl) phosphate,trismethyl phosphate, trisethyl phosphate, triphenyl phosphate,tris(isopropylphenyl) phosphate, and the like, which are phosphateesters used for rigid polyurethane foams or polyisocyanurate foams.

In one embodiment, the premix may include UV inhibitors, scorchinhibitors, premix storage stabilizers, and the like. As a result,various physical properties of the rigid polyurethane foam orpolyisocyanurate foam can be improved.

<Heat Transfer Medium>

In one embodiment, the solvent composition of the present invention issuitable as a heat transfer medium for refrigeration cycle systems, hightemperature heat pump systems, and organic Rankine cycle systems. Insome embodiments, the solvent composition of the present invention issuitable as a cleaning agent for cleaning these cycle systems.

In this specification, “refrigeration cycle system” refers to a steamcompression type refrigeration cycle system comprising elementequipments of at least an evaporator, a compressor, a condenser, anexpansion valve, and is mainly intended for cooling. The expansion valveis a device for throttle expansion of the heat transfer medium and maybe a capillary tube. In addition to the element equipments, therefrigeration cycle system may include an internal heat exchanger, adryer, a liquid separator, an oil recovery device, and anuncondensed-gas separator. The refrigeration cycle system may be used asa refrigerator, an air conditioning system, or a cooler.

In this specification, “high-temperature heat pump cycle system” refersto a steam compression type heat pump cycle system comprising elementequipments of at least an evaporator, a compressor, a condenser, anexpansion valve, and is mainly intended for heating. The expansion valveis a device for throttle expansion of the heat transfer medium and maybe a capillary tube. In addition to the element equipments, thehigh-temperature heat pump cycle system may include an internal heatexchanger, a dryer, a liquid separator, an oil recovery device, and anuncondensed-gas separator. The high-temperature heat pump cycle systemmay be used as a hot water supply system, a steam generation system, aheating device. The high-temperature heat pump cycle system also mayutilize solar thermal energy, industrial waste heat, etc. as a heatsource.

In this specification, “organic Rankine cycle system” refers to aRankine cycle system comprising element equipments of at least anevaporator, an expander, a condenser, and a booster pump, and isintended primarily to convert thermal energy into electrical energy. Inaddition to the element equipments, the organic Rankine cycle system mayinclude an inner heat exchanger, a dryer, a liquid separator, an oilrecovery device, and an uncondensed-gas separator. The organic Rankinecycle system may be used as a power generator for recovering medium andlow temperature heat. The organic Rankine cycle system also may utilizesolar thermal energy, industrial waste heat, etc. as heat source.

<Fire Extinguishing Composition>

Fire extinguishing composition of the present invention includes atleast 1232xd and nonflammable gas other than 1232xd. 1232xd may be1232xd (Z), 1232xd (E), or a mixture of 1232xd (Z) and 1232xd (E).

The nonflammable gas in the fire extinguishing composition may includeat least one selected from, for example, carbon dioxide, nitrogen,helium, argon, krypton, xenon, radon, trifluoromethane, trifluoromethaneiodide, 1,1-dichloro-2,2,2-trifluoroethane,1-chloro-1,2,2,2-trifluoroethane, pentafluoroethane,1,1,1,2,2,3,3-hexafluoropropane, 1,1,1,2,3,3,3-hexafluoropropane,1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2,2,3,3-heptafluoropropane, (E)1,3,3,3-tetrafluoropropene, (E) 1-chloro-3,3,3-trifluoropropene, (Z)1-chloro-3,3,3-trifluoropropene, 2-bromo-3,3,3-trifluoropropene,1-bromo-3,3,3-trifluoropropene, (Z) 1,1,1,4,4,4-hexafluoro-2-butene, (E)1,1,1,4,4,4-hexafluoro-2-butene, dodecafluoro-2-methylpentane-3-one,tetradecafluoro-2,4-dimethylpentane-3-one, andtetradecafluoro-2-methylhexane-3-one.

The nonflammable gas is preferably nonflammable gas having a boilingpoint lower than 1232xd.

The ratio of 1232xd to the sum of 1232xd and the nonflammable gas in thefire extinguishing composition may be, for example, 10 mol % or more and99 mol % or less.

In one embodiment of the fire extinguishing composition of the presentinvention, the nonflammable gas includes carbon dioxide, and the ratioof 1232xd to the sum of 1232xd and the nonflammable gas may be 20 mol %or more and 99 mol % or less.

In one embodiment of the fire extinguishing composition of the presentinvention, the nonflammable gas includes nitrogen, and the ratio of1232xd to the sum of 1232xd and the nonflammable gas may be 20 mol % ormore and 99 mol % or less.

The present invention is described by the following examples, but thepresent invention is not limited to the following examples.

In the following description, FID % refers to the area % as analyzed bythe gas chromatograph of the FID type used as the detector.

<Fluorination of 1230xd>

1. Fluorination of 1230xd in Liquid Phase

Example 1-A1

30 g (0.16 mol) of 97FID %1,2,3,3-tetrachloro-1-propene (1230xd) and40.0 g (2.00 mol, molar ratio of 1230xd/hydrogen fluoride=about 1/12) ofhydrogen fluoride were introduced into a 200-mL stainless-steelautoclave equipped with a condenser circulating 20° C. coolant and apressure gauge and then the autoclave was heated to 120° C. When thepressure exceeded about 4 MPaG, the reaction-generated gas was extractedfrom the needle valve at the outlet of the condenser so as to maintainthe pressure 4.0 MPaG or more and 4.5 MPaG or less. The extracted gaswas passed through a fluorine resin gas washing bottle containing icewater cooled in an ice water bath to absorb acid, and the reactionproduct organic matter was collected by a glass trap in a dry iceacetone bath. After 3 hours from the start of the temperature rise, itwas confirmed that no pressure rise was observed, and then the reactorwas purged, and the extracted gas was collected in the fluorine resingas washing bottle containing ice water cooled in the ice water bath anda glass trap in the dry ice acetone bath. After the reactor was cooled,the reaction solution in the autoclave and the collection by the glasstrap in the dry ice acetone bath were all mixed in the fluorine resingas washing bottle containing ice water, and the combined mixed solutionwas passed through a fluorine resin separation funnel to separate theorganic matter from an aqueous phase and to collect. The amount ofrecovered the organic matter was 22.1 g, and the 1232xd geometric isomerratio in the organic matter was cis:trans=93:7.

Example 1-A2

The reaction was carried out in the same manner as in the example 1-A1except that the reaction temperature was 140° C. The amount of organicmatter recovered was 21.8 g.

Example 1-A3

The reaction was carried out as in the example 1-A1 except that thereaction temperature was 160° C. and the hydrogen fluoride 80.0 g (4.00mol, molar ratio of 1230xd/hydrogen fluoride=about 1/24) was introduced.The amount of organic matter recovered was 19.6 g.

Example 1-A4

Reaction was carried out as in the example 1-A2 except that tin chloride(SnCl₄)3g) was added. The amount of organic matter recovered was 21.8 g.

Example 1-A5

The reaction was carried out in the same manner as in the example 1-A1except that 454 g (2.53 mol) of 97FID %1,2,3,3-tetrachloro-1-propene(1230xd) and 1000.0 g (55.0 mol, molar ratio of 1230xd/hydrogenfluoride=about 1/22) of hydrogen fluoride were introduced into a 2 Lstainless-steel autoclave equipped with a condenser circulating acoolant at 20° C. and a pressure gauge, and then the autoclave washeated to 160° C. The amount of organic matter recovered was 350 g.

The results of gas chromatographic analyses for the Examples 1-A1 to1-A5 are shown in Table 1.

TABLE 1 Hydrogen Recovery Conversion Temperature fluoride amount yieldFID % Example [° C.] [equivalent] Catalyst [g] [%] 1232xd 1231xd 1230xdothers material — — 97.0 3.0 1-A1 120 12 none 22.1 21.7 23.3 10.1 84.81.8 1-A2 140 12 none 21.8 55.8 80.8 13.0 24.1 2.1 1-A3 160 24 none 19.675.6 91.7 3.3 2.8 1.7 1-A4 140 12 SnCl₄ 21.8 41 7 45.5 9.6 42.0 2.9 1-A5160 22 none 350 92.1 92.1 4.1 2.6 1.2

In Table 1, “conversion yield” indicates a simple purity conversionyield of 1232xd calculated according to the following formula.Simple purity conversion yield of 1232xd=100×(recovered organicmatter×1232xdFID %/1232xd molecular weight)/(1230xd chargedamount×1230xd purity/1230xd molecular weight)

In Table 1, “−” indicates that it was not detected.

2. Fluorination of 1230xd in Vapor Phase

Preparation Example 1

Preparation of Fluorinated Activated Alumina

300 g of activated alumina (KHS-46 made by Sumitomo Chemical Co., Ltd.:particle size 4-6 mm, specific surface area 155 m²/g) was measured, andthe powder adhering to the surface was washed with water. After washing,1150 g of 10 mass % hydrofluoric acid was slowly added to the aluminaand stirred, and then the alumina was left to stand for about 4 hours.After washing with water, filtration was carried out, drying was carriedout at room temperature overnight, and then drying was carried out in anelectric furnace at 200° C. for 2 hours. 150 ml of the dried activatedalumina was placed in a stainless-steel (SUS316) reactor tube having aninner diameter of 1 inches and a length of 40 cm, the temperature wasraised to 200° C. in an electric oven while flowing nitrogen at a flowrate of 150 cc/min, and hydrogen fluoride was further flowed at a flowrate of 0.01 g per minute together with nitrogen. Although thetemperature rises as this hydrogen fluoride treatment is carried out,the flow rates of nitrogen and hydrogen fluoride were adjusted so thatthe internal temperature did not exceed 400° C. When the exotherm hadsubsided, the flow rate of nitrogen was lowered to 30 cc/min, the settemperature of the electric furnace was raised by 50° C. every 30minutes, finally raised to 400° C., and the state was maintained for 2hours. In this manner, activated alumina treated with fluorination(hereinafter referred to as Catalyst 1) was prepared.

Preparation Example 2

Preparation of Chrome-Supported Fluorinated Alumina Catalyst

20 mass % chromium chloride aqueous solution was added to the triangularflask, and 100 mL of fluorination treated active alumina prepared inPreparation Example 1 was immersed in the solution, and then held for 3hours. The alumina was filtered and dried under reduced pressure at 70°C. using a rotary evaporator. 100 ml of this chrome-supported aluminawas charged into the cylindrical stainless-steel (SUS316) reactor tubehaving an inner diameter of 1-inch and a length of 40 cm equipped withan electric oven, and the temperature was raised to 200° C. whileflowing nitrogen gas, and when no water outflow was observed, nitrogengas was supplied at a flow rate of 150 cc/min and hydrogen fluoride wassimultaneously supplied at a flow rate of 0.1 g/min, and the flow ratesof nitrogen and hydrogen fluoride were adjusted so that the internaltemperature did not exceed 400° C. When the hot spot due to thefluorination of the charged chromium-supported alumina reached theoutlet end of the reactor tube, the flow rate of the nitrogen waslowered to 30 cc/min, and the set temperature of the electric furnacewas raised by 50° C. every 30 minutes, and finally raised to 400° C. andheld for 2 hours. In this manner, chrome-supported alumina treated withfluorination (hereinafter referred to as Catalyst 2) was prepared.

Preparation Example 3

Preparation of Chrome-Supported Fluorinated Activated Carbon

20 mass % chromium chloride aqueous solution was added to the triangularflask, and the activated carbon 100 ml was immersed in the solution, andthen held for 3 hours. The activated carbon was filtered and dried underreduced pressure at 70° C. using a rotary evaporator. 100 ml of thechrome-supported activated carbon thus obtained was charged into thecylindrical stainless-steel (SUS316) reactor tube having an innerdiameter of 1 inch and a length of 40 cm and equipped with an electricoven, and the temperature was raised to 200° C. while flowing nitrogengas, and at the point when no water outflow was observed, nitrogen gaswas supplied at a flow rate of 150 cc/min and hydrogen fluoride wassimultaneously supplied at a flow rate of 0.1 g/min, and the flow ratesof nitrogen and hydrogen fluoride were adjusted so that the internaltemperature did not exceed 400° C. When the hot spot of the chargedchrome-supported activated carbon by fluorination reached the outlet endof the reactor tube, the flow rate of nitrogen was lowered to 30 cc/min,and the set temperature of the electric furnace was raised by 50° C.every 30 minutes, and finally raised to 400° C. and held for 2 hours.Thus, chrome-supported fluorinated activated carbon treated withfluorination (hereinafter referred to as Catalyst 3) was prepared.

Example 1-B1

50 ml of the catalyst prepared in Preparation Example 2 was charged intoa 1 inch×40 cm long stainless-steel (SUS316) reaction tube equipped withan electric oven, and the temperature of the reaction tube was raised to250° C. while flowing nitrogen gas at a flow rate of about 30 cc/min.Nitrogen-feed was stopped and a raw material, that is, vaporized1,2,3,3-tetrachloro-1-propene (1230xd) was introduced at a flow rate of0.20 g/min and hydrogen fluoride at a flow rate of 0.20 g/min. Thepressure was atmospheric pressure and the contact time with the catalystwas 12 seconds. When the flow rate was stabilized, 100 ml ice water trapcooled with ice water was installed at the outlet of the reaction tube,and the organic matter was recovered for about 30 minutes and thebyproduct acid content was absorbed, and the weight recovery rate wascalculated. The organic components subjected to acid removal wereanalyzed by gas chromatography. The composition of the recoveredcomponents and the conversion rate of the raw material were calculated,and the results are shown in Table 2. The calculation methods of theweight recovery rate and the raw material conversion rate are asfollows.Weight recovery rate:100×(increased amount of ice water traps [g])/(rawmaterial [g]+hydrogen fluoride [g])Feed conversion rate:100×(1−raw material composition FID % in recoveredorganic matter/raw composition FID %)

Example 1-B2

The same procedure as in Example 1-B1 was carried out except that thetemperature in the reactor tube was set to 200° C.

Example 1-B3

The same procedure as in Example 1-B1 was carried out except that thetemperature in the reactor tube was set to 300° C.

Example 1-B4

The same procedure as in Example 1-B1 was carried out except that thetemperature in the reactor tube was set to 350° C.

The results of Examples 1-B1 to 1-B4 are shown in Table 2.

TABLE 2 Hydrogen Recovery fluoride Temperature amount FID % ExampleCatalyst [equivalent] [° C.] [wt %] 1232xd 1231xd 1230xd others material— — 98.6 1.4 1 B1 Catalyst 2 10 250 97.6 90.0 5.1 2.5 2.4 1-B2 Catalyst2 10 200 94.3 84.4 7.3 6.8 1.5 1-B3 Catalyst 2 10 300 93.9 87.8 5.6 3.83.3 1-B4 Catalyst 2 10 350 96.2 85.3 6.9 3.8 4.0

Referring to Table 2, it can be seen that 1232xd can be synthesized byfluorination of 1230xd in the range of 200° C. or more and 350° C. orless.

Example 1-B5

The same procedure as in Example 1-B1 were carried out except thatCatalyst 3 was charged instead of Catalyst 2.

Example 1-B6

The same procedure as in Example 1-B1 was carried out except thatCatalyst 1 was charged instead of Catalyst 2.

Example 1-B7

The same procedure as in Example 1-B1 was carried out except thatactivated carbon (Shirasagi G2X4/6-1) 50 ml was charged as a fillerinstead of the catalyst 2.

The results of Example 1-B1, Example 1-B5 to Example 1-B7 are shown inTable 3.

TABLE 3 Hydrogen fluoride Temperature Recovery FID % Example Catalyst[equivalent] [° C.] amount 1232xd 1231xd 1230xd others material — — 98.61.4 1-B1 Catalyst 2 10 250 97.6 90.0 5.1 2.5 2.4 1-B5 Catalyst 3 10 25098.5 85.0 4.3 2.0 8.7 1-B6 Catalyst 1 10 250 91.3 79.5 9.5 8.8 2.3 1-B7none 10 250 98.7 9.0 21.3 54.1 15.6<Synthesis of 240 da>

Example 2-1

A 2 L three-neck flask equipped with a thermometer, an inflow pipe forinflow of liquids, and a dimroth cooling tube was charged with 35 g (10mol %) of powdery aluminium chloride and 1275 g (10.7 mol) ofchloroform, and the flask was sealed with nitrogen. Thereafter, theflask was heated to an internal temperature of about 60° C. by an oilbath, 256 g (2.64 mol) of 1,2-dichloroethylene was introduced from theinflow pipe over 2 hours, and then stirred at 60° C. for 30 minutes toterminate the reaction. The reaction solution was cooled to roomtemperature, washed with 500 ml of 5 mass % hydrogen chloride water, andan organic phase was dried with a molecular sieve, and then the excesschloroform was separated by an evaporator. As a result, 505 g of 240 dacrude product having a purity of 98FID % (a purity conversion yield of86.5% based on 1,2-dichloroethylene) was recovered.

Example 2-2

The same procedure as in Example 2-1 was carried out except that 7.3 g(20 mol %) of aluminium chloride, 31 g (0.26 mol) of chloroform and 100g (1.0 mol) of 1,2-dichloroethylene were used. Thus, 50 g of 240 dacrude product having a purity of 92FID % (a purity conversion yield of80.1% based on chloroform) was recovered. The other components of the240 da crude product were heptachloropentane, except for 240 da.

Examples 2-3

The same procedure as in Example 2-1 was carried out except that 7.3 g(20 mol %) of aluminium chloride, 31 g (0.26 mol) of chloroform and 25 g(0.26 mol) of 1,2-dichloroethylene were used. As a result, 44 g of 240da crude product having a purity of 96FID % (a purity conversion yieldof 75.2% based on 1,2-dichloroethylene) was recovered. The othercomponents of the 240 da crude product were heptachloropentane, exceptfor 240 da.

<Synthesis of 1230xd>

Example 3

A 2 L three-neck flask equipped with a thermometer, an inflow pipe forinflow of liquids, and a dimroth cooling tube through which water wasflowed was charged with 500 g (2.26 mol) of the 240 da crude productsynthesized in Examples 2-1 and 3.0 g of tetrabutylammonium bromide, andthe flask was cooled to about 10° C. in an ice water bath. 550 g (3.4mol, 1.5 eq) of 25 mass % sodium hydroxide aqueous solution was addeddropwise over 2 hours through a dropping funnel, followed by stirring atroom temperature of about 20° C. for 18 hours. 500 ml of 10 mass %hydrogen chloride water was added to the reaction solution, followed bywashing with water, washing with saturated hydrogen carbonate water, anddrying with a molecular sieve. As a result, 410 g of 1230xd crudeproduct having a purity of 97FID % was obtained.

<Detergency Test>

Example 4

Test pieces of SUS-316L (2.8 mm×10 mm×30 mm) were immersed in the oilshown in Table 4 to attach the oil. They were immersed in 10 ml of thesolvent shown in Table 4 for 30 seconds, and then air drying wasperformed at room temperature (23° C.) for 2 minutes. The test piecesafter drying were visually observed, and the detergency of each of themwas evaluated according to the following criteria.

⊚: Very good. The oil is completely removed.

◯: Good. Although some oil scale is observed, it has been largelyremoved.

X: Poor. There is considerable oil remaining.

The results are shown in Table 4.

TABLE 4 Detergency Example Solvent Type of oil evaluation 4-11232xd(Z):1232xd(E) = Press working ⊚ 93:7 (molar ratio) oil A 4-21232xd(Z):1232xd(E) = Press working ⊚ 93:7 (molar ratio) oil B 4-31232xd(Z):1232xd(E) = Working ⊚ 93:7 (molar ratio) oil A 4-41232xd(Z):1232xd(E) = Working ⊚ 93:7 (molar ratio) oil B 4-51232xd(Z):1232xd(E) = Rust preventive ⊚ 93:7 (molar ratio) oil 4-61232xd(Z):1232xd(E) = Mineral oil ⊚ 93:7 (molar ratio) 4-71232xd(Z):1232xd(E) = Silicone oil ⊚ 93:7 (molar ratio) 4-81232xd(Z):1232xd(E) = Press working ⊚ 93:7 (molar ratio) oil A 4-31232xd(Z) Press working ⊚ oil A

In Table 4, the types of oils are as follows.

Press working oil A: PG-3246 manufactured by Nihon Kohsakuyu Co., Ltd.

Press working oil B: PG-3740 manufactured by Nihon Kohsakuyu Co., Ltd.

Working oil Tool A: CF-879 manufactured by Nihon Kohsakuyu Co., Ltd.

Working oil Tool B: C-4115 manufactured by Nihon Kohsakuyu Co., Ltd.

Rust preventive oil: P-5960 manufactured by Nihon Kohsakuyu Co., Ltd.

Mineral oil: Compressor oil manufactured by Sumitomo Lubricant Co., Ltd.

Silicone Oil: KF-96-100CS manufactured by Shin-Etsu Chemical Co., Ltd.

<Solubility Test>

Example 5

10 g of the solvent shown in Table 5 and 1 g of the oil shown in Table 5were added to a 50 ml glass sample bottle and shaken and mixed. This wasallowed to stand in a laboratory controlled at room temperature (23°C.). After 30 minutes, the state of the solution was visually observed,and the solubility was evaluated according to the following criteria.

A: Very good. The oil is completely dissolved and homogeneous.

B: Some good. Some of the oil is dissolved, but two-phase separation isobserved.

C: Poor. There is no oil dissolution and two-phase separation isobserved.

The results are shown in Table 5.

TABLE 5 Solubility Example Type of oil evaluation 5-11232xd(Z):1232xd(E) = Press working A 93:7 (molar ratio) oil A 5-21232xd(Z):1232xd(E) = Press working A 93:7 (molar ratio) oil B 5-31232xd(Z):1232xd(E) = Working A 93:7 (molar ratio) oil A 5-41232xd(Z):1232xd(E) = Working A 93:7 (molar ratio) oil B 5-51232xd(Z):1232xd(E) = Rust preventive A 93:7 (molar ratio) oil 5-81232xd(Z):1232xd(E) = Mineral oil A 93:7 (molar ratio) 5-71232xd(Z):1232xd(E) = Silicone oil A 93:7 (molar ratio)

In Table 5, the types of oils are as follows.

Press working oil A: PG-3246 manufactured by Nihon Kohsakuyu Co., Ltd.

Press working oil B: PG-3740 manufactured by Nihon Kohsakuyu Co., Ltd.

Working oil A: CF-879 manufactured by Nihon Kohsakuyu Co., Ltd.

Working oil B: C-4115 manufactured by Nihon Kohsakuyu Co., Ltd.

Rust preventive oil: P-5960 manufactured by Nihon Kohsakuyu Co., Ltd.

Mineral oil: Compressor oil manufactured by Sumitomo Lubricant Co., Ltd.

Silicone Oil: KF-96-100CS manufactured by Shin-Etsu Chemical Co., Ltd.

Example 6

All solvent and oil mixtures used in Example 5 were combined andrecovered. Simple distillation was carried out to obtain 1232xd having apurity of 99GC % from the recovered mixture.

What is claimed is:
 1. A solvent composition comprising:1,2-dichloro-3,3-difluoro-1-propene, wherein the1,2-dichloro-3,3-difluoro-1-propene contains both ofcis-1,2-dichloro-3,3-difluoro-1-propene andtrans-1,2-dichloro-3,3-difluoro-1-propene, and wherein a molar ratio ofthe cis-1,2-dichloro-3,3-difluoro-1-propene to thetrans-1,2-dichloro-3,3-difluoro-1-propene in the solvent is 50.00:50.00to 99.99:0.01.
 2. The solvent composition according to claim 1, whereinthe molar ratio of the cis-1,2-dichloro-3,3-difluoro-1-propene to thetrans-1,2-dichloro-3,3-difluoro-1-propene in the solvent is 60.00:40.00to 99.99:0.01.
 3. The solvent composition according to claim 1, whereinthe molar ratio of the cis-1,2-dichloro-3,3-difluoro-1-propene to thetrans-1,2-dichloro-3,3-difluoro-1-propene in the solvent is 70.00:30.00to 99.99:0.01.
 4. The solvent composition according to claim 1, whereinthe molar ratio of the cis-1,2-dichloro-3,3-difluoro-1-propene to thetrans-1,2-dichloro-3,3-difluoro-1-propene in the solvent is 80.00:20.00to 99.99:0.01.
 5. The solvent composition according to claim 1, whereinthe molar ratio of the cis-1,2-dichloro-3,3-difluoro-1-propene to thetrans-1,2-dichloro-3,3-difluoro-1-propene in the solvent is 90.00:10.00to 99.99:0.01.
 6. The solvent composition according to claim 1, whereinthe molar ratio of the cis-1,2-dichloro-3,3-difluoro-1-propene to thetrans-1,2-dichloro-3,3-difluoro-1-propene in the solvent is 93.00:7.00to 95.00:5.00.
 7. The solvent composition according to claim 1, furthercomprising: at least one selected from a group consisting of1,2,3-trichloro-3-fluoro-1-propene, an organic compound and an additiveagent, wherein the organic compound is at least one selected from agroup consisting of hydrocarbons, alcohols, ketones, ethers, esters,chlorocarbons, HFCs, and HFEs, and the additive agent is at least oneselected from a group consisting of a stabilizer, a surfactant, and aflame retardant.
 8. The solvent composition according to claim 7,wherein a content of the 1,2,3-trichloro-3-fluoro-1-propene in thesolvent composition is 0.001 mass % or more and 40 mass % or less whenthe solvent composition comprises the1,2,3-trichloro-3-fluoro-1-propene.
 9. An aerosol compositioncomprising: the solvent composition according to claim 1; and aninjection gas.
 10. A cleaning method of a material, comprising: a stepof contacting the material with the solvent composition according toclaim
 1. 11. A method for producing a lubricant solution comprising:diluting a lubricant with the solvent composition according to claim 1.12. A method for producing a material with a lubricant, comprising:coating the lubricant solution according to claim 11 to a surface of thematerial; and forming a coating film including the lubricant on thesurface of the material by volatilizing the solvent composition or theaerosol composition from the material.
 13. A cleaning agent comprisingthe solvent composition according to claim
 1. 14. A draining agentcomprising the solvent composition according to claim
 1. 15. A foamingagent comprising the solvent composition according to claim
 1. 16. Aheat transfer medium comprising the solvent composition according toclaim
 1. 17. An organic Rankine cycle system using the heat transfermedium according to claim
 16. 18. A high-temperature heat pump cyclesystem using the heat transfer medium according to claim
 16. 19. Arefrigeration cycle system using the heat transfer medium according toclaim
 16. 20. A fire extinguishing composition comprising: the solventcomposition according to claim 1; and at least a nonflammable gas exceptfor 1,2-dichloro-3,3-difluoro-1-propene.